DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Shuaishuai; Fifield, Leonard S.; Bowler, Nicola
Cross-linked polyethylene (XLPE) cable insulation material undergoes simultaneous, accelerated thermal and gamma-radiation aging to simulate the long-term aging environment within nuclear power plants (NPPs). A variety of materials characterization tests, including scanning electron microscopy, thermo-gravimetric analysis, differential scanning calorimetry, oxidation induction time, gel-fraction and dielectric properties measurement, are conducted on pristine and differently aged XLPE samples. A preliminary model of one possible aging mechanism of XLPE cable insulation material under gamma radiation at elevated temperature of 115 °C is suggested.
Crosslinked polyethylene foams, via EB radiation
NASA Astrophysics Data System (ADS)
Cardoso, E. C. L.; Lugão, A. B.; Andrade E. Silva, L. G.
1998-06-01
Polyethylene foams, produced by radio-induced crosslinking, show a smooth and homogeneous surface, when compared to chemical crosslinking method using peroxide as crosslinking agent. This process fosters excellent adhesive and printability properties. Besides that, closed cells, intrinsic to theses foams, imparts opitmum mechanical, shocks and insulation resistance, indicating these foams to some markets segments as: automotive and transport; buoyancy, flotation and marine: building and insulation: packaging: domestic sports and leisure goods. We were in search of an ideal foam, by adding 5 to 15% of blowing agent in LDPE. A series of preliminary trials defined 203° C as the right blowing agent decomposition temperature. At a 22.7 kGy/dose ratio, the lowest dose for providing an efficient foam was 30 kGy, for a formulation comprising 10% of azodicarbonamide in LDPE, within a 10 minutes foaming time.
Treeing phenomenon of thermoplastic polyethylene blends for recyclable cable insulation materials
NASA Astrophysics Data System (ADS)
Li, Lunzhi; Zhang, Kai; Zhong, Lisheng; Gao, Jinghui; Xu, Man; Chen, Guanghui; Fu, Mingli
2017-02-01
Owing to its good recyclability and low processing energy consumption, non-crosslinked polyethylene blends (e.g. LLDPE-HDPE blends) are considered as one of potential environmental-friendly substitutions for crosslinked polyethylene (XLPE) as cable insulation material. Although extensive work has been performed for measuring the basic dielectric properties, there is a lack of the investigations on the aging properties for such a material system, which hinders the evaluation of reliability and lifetime of the material for cable insulation. In this paper, we study the electric aging phenomenon of 0.7LLDPE-0.3HDPE blending material by investigating the treeing behavior, and its comparison with XLPE and LLDPE. Treeing tests show that the 0.7LLDPE-0.3HDPE blends have lower probability for treeing as well as smaller treeing dimensions. Further thermal analysis and microstructure study results suggest that the blends exhibit larger proportion of thick lamellae and higher crystallinity with homogeneously-distributed amorphous region, which is responsible for good anti-treeing performance. Our finding provides the evidence that the 0.7LLDPE-0.3HDPE blends exhibits better electric-aging-retardance properties than XLPE, which may result in a potential application for cable insulation.
New developments in the field of high voltage and extra-high voltage cables
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jocteur, R.
1990-04-01
In this paper, the author presents the developments in progress at the present time in France concerning the high voltage (HV) and extra-high voltage (EHV) cables with synthetic insulation and their accessories up to the 500 kV range. The authors have adopted a maximum operating field strength approaching 16 kV/mm (405 V/mil) for low density polyethylene (LDPE) insulated cables. The on-going studies should allow to bring the maximum operating field strength for crosslinked polyethylene (XLPE) insulation from 7 to 10 kV/mm (180 to 255 V/mil) and cables could be manufactured more economically with this material.
Effects of Electrical Insulation Breakdown Voltage And Partial Discharge
NASA Astrophysics Data System (ADS)
Bahrim, F. S.; Rahman, N. F. A.; Haris, H. C. M.; Salim, N. A.
2018-03-01
During the last few decades, development of new materials using composite materials has been of much interest. The Cross-linked Polyethylene (XLPE) which is insulated power cables has been widely used. This paper describes the theoretical analysis, fundamental experiments and application experiments for the XLPE cable insulation. The composite that has been tested is a commercial XLPE and Polypropylene with 30% fiber glass. The results of breakdown strength and partial discharge (PD) behavior described the insulating performance of the composite.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Shuaishuai; Fifield, Leonard S.; Bowler, Nicola
Aging mechanisms and a nondestructive aging indicator of filled cross-linked polyethylene (XLPE) cable insulation material used in nuclear power plants (NPPs) are studied. Using various material characterization techniques, likely candidates and functions for the main additives in a commercial filled-XLPE insulation material have been identified. These include decabromodiphenyl ether and Sb2O3 as flame retardants, ZnS as white pigment and polymerized 1,2-dihydro-2,2,4-trimethylquinoline as antioxidant. Gas chromatography-mass spectrometry, differential scanning calorimetry, oxidation induction time and measurements of dielectric loss tangent are utilized to monitor property changes as a function of thermal and radiation exposure of the cable material. Small-molecular-weight hydrocarbons are evolvemore » with gamma radiation aging at 90 °C. The level of antioxidant decreases with aging by volatilization and chemical reaction with free radicals. Thermal aging at 90 °C for 25 days or less causes no observable change to the cross-linked polymer structure. Gamma radiation causes damage to crystalline polymer regions and introduces defects. Dielectric loss tangent is shown to be an effective and reliable nondestructive indicator of the aging severity of the filled-XLPE insulation material.« less
NASA Astrophysics Data System (ADS)
Fan, Yang; Qi, Yang; Bing, Gao; Rong, Xia; Yanjie, Le; Iroegbu, Paul Ikechukwu
2018-03-01
Water tree is the predominant defect in high-voltage crosslinked polyethylene cables. The microscopic mechanism in the discharge process is not fully understood; hence, a drawback is created towards an effective method to evaluate the insulation status. In order to investigate the growth of water tree, a plasma-chemical model is developed. The dynamic characteristics of the discharge process including voltage waveform, current waveform, electron density, electric potential, and electric field intensity are analyzed. Our results show that the distorted electric field is the predominant contributing factor of electron avalanche formation, which inevitably leads to the formation of pulse current. In addition, it is found that characteristic parameters such as the pulse width and pulse number have a great relevance to the length of water tree. Accordingly, the growth of water tree can be divided into the initial stage, development stage, and pre-breakdown stage, which provides a reference for evaluating the deteriorated stages of crosslinked polyethylene cables.
NASA Astrophysics Data System (ADS)
Sosnowski, M.; Eager, G. S., Jr.
1983-06-01
Threshold voltage of oil-impregnated paper insulated cables are investigaed. Experimental work was done on model cables specially manufactured for this project. The cables were impregnated with mineral and with synthetic oils. Standard impulse breakdown voltage tests and impulse voltage breakdown tests with dc prestressing were performed at room temperature and at 1000C. The most important result is the finding of very high level of threshold voltage stress for oil-impregnated paper insulated cables. This threshold voltage is approximately 1.5 times higher than the threshold voltage or crosslinked polyethylene insulated cables.
NASA Astrophysics Data System (ADS)
Zhang, Ling; Khani, Mohammad M.; Krentz, Timothy M.; Huang, Yanhui; Zhou, Yuanxiang; Benicewicz, Brian C.; Nelson, J. Keith; Schadler, Linda S.
2017-03-01
Incorporating inorganic nanoparticles (NPs) into polymer matrices provides a promising solution for suppressing space charge effects that can lead to premature failure of electrical insulation used in high voltage direct current engineering. However, realizing homogeneous NP dispersion is a great challenge especially in high-molecular-weight polymers. Here, we address this issue in crosslinked polyethylene by grafting matrix-compatible polymer brushes onto spherical colloidal SiO2 NPs (10-15 nm diameter) to obtain a uniform NP dispersion, thus achieving enhanced space charge suppression, improved DC breakdown strength, and restricted internal field distortion (≤10.6%) over a wide range of external DC fields from -30 kV/mm to -100 kV/mm at room temperature. The NP dispersion state is the key to ensuring an optimized distribution of deep trapping sites. A well-dispersed system provides sufficient charge trapping sites and shows better performance compared to ones with large aggregates. This surface ligand strategy is attractive for future nano-modification of many engineering insulating polymers.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fifield, Leonard S.; Correa, Miguel
Cross-linked polyethylene (XLPE) is the most common cable insulation found in nuclear containment, and is therefore a priority material for investigation of long term aging effect from elevated temperature combined with gamma radiation exposure. Prior work has identified the possibility of anomalous aging behavior in XLPE such as the inverse temperature effect in which radiation exposure is more damaging at lower temperatures than at higher temperatures. We explored simultaneous aging of XLPE insulation from modern Firewall® III nuclear cables at 60, 90, and 115 °C, at gamma dose rates from 116 to 540 Gy/h, for exposure periods up to 25more » d. XLPE samples exposed in this way were characterized using the percent gel and uptake factor method. For the conditions and material examine, degradation behavior was seen to track proportionally with increasing temperature, rather than to exhibit greater degradation at lower temperatures. Ongoing work including similar aging at 25 °C and characterization of the XLPE samples using other methods will further elucidate these initial results« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Correa, Miguel; Huang, Qian; Fifield, Leonard S.
Cross-linked polyethylene (XLPE) cable insulation samples were exposed to heat and gamma radiation at a series of temperatures, dose rates, and exposure times to evaluate the effects of these variables on material degradation. The samples were tested using the solvent incubation method to collect gel fraction and uptake factor data in order to assess the crosslinking and chain scission occurring in polymer samples with aging. Consistent with previous reports, gel fraction values were observed to increase and uptake factor values to decrease with radiation and thermal exposure. The trends seen were also more prominent as exposure time increased, suggesting thismore » to be a viable method of tracking structural changes in the XLPE-insulated cable material over extended periods. For the conditions explored, the cable insulation material evaluated did not indicate signs of anomalous aging such as inverse temperature effect in which radiation-induced aging is more severe at lower temperature. Ongoing aging under identical radiation conditions and at lower temperature will further inform conclusions regarding the importance of inverse temperature effects for this material under these conditions.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bahder, G.; Bopp, L.A.; Eager, G.S.
This report covers the continuation of the work to develop technology to manufacture chemically crosslinked polyethylene insulated power cables in the ac voltage range of 138 kV to 345 kV having insulation thicknesses approximately equal to that of oil impregnated paper insulated cables. It also incorporates the development of field molded splices and terminations for new high voltage stress 138 kV cables. After reviewing the main equipment elements, incorporated in the pilot extrusion line, the special features of this system are noted and a step-by-step description of the cable extrusion process is given. Optimization of the process and introduction ofmore » modifications in the equipment culminated with the production of 138 kV cables. Results of laboratory tests to demonstrate the high quality of the cables are given. The development of molded splices and molded stress control cones was initiated with the work on model cables and followed by the making of splices and terminations on 138 kV cables. The molded components are made with the same purified insulating compound as used in the manufacture of the cables. Both the molded splices and the molded stress control cones have been fully tested in the laboratory. Following the completion of the development of the 138 kV cable a high stress 230 kV crosslinked polyethylene cable was developed and optimized. A full evaluation program similar to the one utilized on the 138 kV cable was carried out. Subsequently, work to develop a 345 kV high voltage stress cable, having insulation thickness of 1.02'' was undertaken. 345 kV cables were successfully manufactured and tested. However, additional work is required to further optimize the quality of this cable.« less
Radiation Resistant Electrical Insulation Materials for Nuclear Reactors: Final Report
DOE Office of Scientific and Technical Information (OSTI.GOV)
Duckworth, Robert C.; Aytug, Tolga; Paranthaman, M. Parans
The instrument and control cables in future nuclear reactors will be exposed to temperatures, dose rates, and accumulated doses exceeding those originally anticipated for the 40-year operational life of the nuclear power plant fleet. The use of nanocomposite dielectrics as insulating material for such cables has been considered a route to performance improvement. In this project, nanoparticles were developed and successfully included in three separate material systems [cross-linked polyvinyl alcohol (PVA/XLPVA), cross-linked polyethylene (PE/XLPE), and polyimide (PI)], and the chemical, electrical, and mechanical performance of each was analyzed as a function of environmental exposure and composition. Improvements were found inmore » each material system; however, refinement of each processing pathway is needed, and the consequences of these refinements in the context of thermal, radiation, and moisture exposures should be evaluated before transferring knowledge to industry.« less
Morphology of Thermally Degraded PU and Irradiated PE
NASA Astrophysics Data System (ADS)
Harris, Douglas; Gillen, Kenneth; Celina, Mathias; Assink, Roger
2001-03-01
Several 1H and 13C NMR techniques have been applied to study the morphology and chemical structure of thermally degraded polyurethane rubber and irradiated polyethylene cable insulation. The combination of heat and presence of air results in oxidation of the hydroxyl-terminated polybutadiene/isophorone diisocyanate polyurethane and the gel content increases. The oxidation is inhomogeneous: pristine regions remain with a length scale of approximately 20 nm. The morphology and oxidation products were characterized by 1H spin diffusion with 13C detection. In addition, dynamics were probed with 1H and 2D WISE experiments. Radiation of cross-linked polyethylene cable insulation obeys anomalous aging behavior where lower temperature can result in a greater loss in ultimate tensile elongation. Annealing of the irradiated polyethylene allows significant recovery of mechanical properties. Analysis of 13C NMR data was used to study this "Lazarus effect" and the inverse temperature relationship. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04-94AL8500.
Morsy, M A; Shwehdi, M H
2006-03-01
Electron spin resonance (ESR) study is carried out to characterize thermal endurance of insulating materials used in power cable industry. The presented work provides ESR investigation and evaluation of widely used cable insulation materials, namely polyvinyl chloride (PVC) and cross-linked polyethylene (XLPE). The results confirm the fact that PVC is rapidly degrades than XLPE. The study also indicates that colorants and cable's manufacturing processes enhance the thermal resistance of the PVC. It also verifies the powerfulness and the importance of the ESR-testing of insulation materials compared to other tests assumed by International Electrotechnical Commission (IEC) Standard 216-procedure, e.g. weight loss (WL), electric strength (ES) or tensile strength (TS). The estimated thermal endurance parameters by ESR-method show that the other standard methods overestimate these parameters and produce less accurate thermal life time curves of cable insulation materials.
NASA Astrophysics Data System (ADS)
Kozitsyna, M. V.; Trufanova, N. M.
2017-01-01
Today the process of coextrusion is the most technological in the cable production with cross-linked polyethylene, composed of two or more layers of polymeric insulation. Since the covering technology is a simultaneous imposition of all necessary layers (two semiconducting shields on the insulation and conductor and one - on insulation), the main focus of this study is the analysis of significance of various factors influence on stratified flows characteristics. This paper has considered the flow of two abnormally viscous liquids in the cable head. The problem has been solved through a three-dimensional statement by applying the finite element method in the Ansys software package. The influence has been estimated by varying the rheological properties of materials to create all necessary layers thickness.
NASA Astrophysics Data System (ADS)
Zha, Jun-Wei; Yan, Hong-Da; Li, Wei-Kang; Dang, Zhi-Min
2016-11-01
Polypropylene (PP) has become one promising material to potentially replace the cross-link polyethylene used for high voltage direct current cables. Besides the isotactic polypropylene, the block polypropylene (b-PP) and random polypropylene (r-PP) can be synthesized through the copolymerization of ethylene and propylene molecules. In this letter, the effect of morphology and crystalline phases on the insulating electrical properties of PP was investigated. It was found that the introduction of polyethylene monomer resulted in the formation of β and γ phases in b-PP and r-PP. The results from the characteristic trap energy levels indicated that the β and γ phases could induce deep electron traps which enable to capture the carriers. And the space charge accumulation was obviously suppressed. Besides, the decreased electrical conductivity was observed in b-PP and r-PP. It is attributed to the existence of deep traps which can effectively reduce the carrier mobility and density in materials.
Electrical conduction of a XLPE nanocomposite
NASA Astrophysics Data System (ADS)
Park, Yong-Jun; Sim, Jae-Yong; Lim, Kee-Joe; Nam, Jin-Ho; Park, Wan-Gi
2014-07-01
The resistivity, breakdown strength, and formation of space charges are very important factors for insulation design of HVDC cable. It is known that a nano-sized metal-oxide inorganic filler reduces the formation of space charges in the polymer nanocomposite. Electrical conduction of cross-linked polyethylene(XLPE) nanocomposite insulating material is investigated in this paper. The conduction currents of two kinds of XLPE nanocomposites and XLPE without nano-filler were measured at temperature of 303 ~ 363 K under the applied electric fields of 10 ~ 50 kV/mm. The current of the nanocomposite specimen is smaller than that of XLPE specimen without nano-filler. The conduction mechanism may be explained in terms of Schottky emission and multi-core model.
Interrelation of electret properties of polyethylene foam from the method of cross-linking
NASA Astrophysics Data System (ADS)
Gilmanov, I. R.; Galikhanov, M. F.; Gilmanova, A. R.
2017-09-01
The electret properties of chemically cross-linked polyethylene foam and physically cross-linked polyethylene foam have been studied. It has been shown that chemically cross-linked polyethylene foam has higher surface potential, effective surface charge density and electric field strength compared to physically bonded polyethylene foam. This is due to the presence of molecules and fragments of dicumyl peroxide, which can play the role of traps for injection charge carriers, a greater degree of cross-linking and with the oxidation of polyethylene, which occurs during irradiation during physical cross-linking. When the foam is deformed, its electret properties are reduced, and when the volume is relaxed, they are restored. This is due to the partial mutual compensation of homo- and heterocharge during compression and the return of the structure of the gas-filled polymer to its former position when the load is removed.
Cross-linked compared with historical polyethylene in THA: an 8-year clinical study.
Geerdink, Carel H; Grimm, Bernd; Vencken, Wendy; Heyligers, Ide C; Tonino, Alphons J
2009-04-01
Wear particle-induced osteolysis is a major cause of aseptic loosening in THA. Increasing wear resistance of polyethylene (PE) occurs by increasing the cross-link density and early reports document low wear rates with such implants. To confirm longer-term reductions in wear we compared cross-linked polyethylene (irradiation in nitrogen, annealing) with historical polyethylene (irradiation in air) in a prospective, randomized clinical study involving 48 patients who underwent THAs with a minimum followup of 7 years (mean, 8 years; range, 7-9 years). The insert material was the only variable. The Harris hip score, radiographic signs of osteolysis, and polyethylene wear were recorded annually. Twenty-three historical and 17 moderately cross-linked polyethylene inserts were analyzed (five patients died, three were lost to followup). At 8 years, the wear rate was lower for cross-linked polyethylene (0.088 +/- 0.03 mm/year) than for the historical polyethylene (0.142 +/- 0.07 mm/year). This reduction (38%) did not diminish with time (33% at 5 years). Acetabular cyst formation was less frequent (39% versus 12%), affected fewer DeLee and Charnley zones (17% versus 4%), and was less severe for the cross-linked polyethylene. The only revision was for an aseptically loose cup in the historical polyethylene group. Moderately cross-linked polyethylene maintained its wear advantage with time and produced less osteolysis, showing no signs of aging at mid-term followup. Level I, therapeutic study. See Guidelines for Authors for a complete description of levels of evidence.
Hirose, H
1997-01-01
This paper proposes a new treatment for electrical insulation degradation. Some types of insulation which have been used under various circumstances are considered to degrade at various rates in accordance with their stress circumstances. The cross-linked polyethylene (XLPE) insulated cables inspected by major Japanese electric companies clearly indicate such phenomena. By assuming that the inspected specimen is sampled from one of the clustered groups, a mixed degradation model can be constructed. Since the degradation of the insulation under common circumstances is considered to follow a Weibull distribution, a mixture model and a Weibull power law can be combined. This is called The mixture Weibull power law model. By using the maximum likelihood estimation for the newly proposed model to Japanese 22 and 33 kV insulation class cables, they are clustered into a certain number of groups by using the AIC and the generalized likelihood ratio test method. The reliability of the cables at specified years are assessed.
Gamma-irradiated cross-linked LDPE foams: Characteristics and properties
NASA Astrophysics Data System (ADS)
Cardoso, E. C. L.; Scagliusi, S. R.; Parra, D. F.; Lugão, A. B.
2013-03-01
Foamed polymers are future materials, as they are increasingly considered "green materials" due to their interesting properties at very low consumption of raw materials. They can be used to improve appearance of insulation structures, thermal and acoustic insulation, core materials for sandwich panels, fabrication of furniture and flotation materials or to reduce costs involving materials. Low-density polyethylene is widely used because of its excellent properties, such as softness, elasticity, processibility and insulation. In general, cross-linking is often applied to improve the thermal and mechanical properties of polyethylene products, due to the formation of a three-dimensional network. In particular for the production of PE foams, cross-linking is applied prior the expansion to control bubble formation, cell characteristics and final properties of the foam. However, the usual production process of PE foams is a process in which a gaseous blowing agent is injected into a melted thermoplastic polymer, under pressure, to form a solution between blowing agent and melted polymer. An extrusion system is provided for foaming the polymer, supplied to an extruder and moving through a rotating screw. The pressure must be high enough to keep the gas blowing agent (or foaming agent) in the solution with the melt. The foaming agent is then diffused and dissolved in the molten material to form a single-phase solution. In the present work carbon dioxide was used as the bowing agent, a chemically stable and non-toxic gas, with good diffusion coefficient; gas pressure used varied within a 20-40 bar range. Some requirements for physical foaming are required, as low friction heat generation, homogeneous melt temperature distribution, melt temperature at die exit just above crystallization temperature (die) and high melt strength during expansion. This work studied foams properties gamma-irradiated within 0, 10, 15, 20, 25, and 30 kGy, from a LDPE exhibiting 2.6 g/10 min Melt Index. Accomplished tests: DSC, gel-fraction, swelling ratio in various solvents, rheological measurements, infra-red spectroscopy and melt strength. It was verified that within a given radiation dose range; the material exhibited an optimization in viscoelastic properties, providing the desired melt strength range for obtaining foams.
Estok, Daniel M; Bragdon, Charles R; Plank, Gordon R; Huang, Anna; Muratoglu, Orhun K; Harris, William H
2005-02-01
Quantification of creep of highly cross-linked polyethylene would enable separation of creep from wear when evaluating femoral head penetration into polyethylene. We compared creep magnitude of a highly cross-linked versus conventional polyethylene in the laboratory. Twelve acetabular liners of each material were tested, 6 of which had a 32-mm inner diameter (ID) and 6 had 28-mm ID. Creep was measured using coordinate measuring machines during loading at 2 Hz without motion to 4 million cycles. Penetration into 32-mm ID conventional liners reached 97 microm versus 107 microm for highly cross-linked material, not significant. Penetration into 28-mm conventional liners was 132 microm versus 155 microm for highly cross-linked material (P = .017). Ninety percent of the creep had occurred by 2.5 million cycles.
Kim, Young-Hoo; Park, Jang-Won; Kim, Jun-Shik; Lee, June-Hyung
2015-11-01
Concern regarding osteolysis attributable to polyethylene wear after TKA, particularly in younger patients, has prompted the introduction of highly crosslinked-remelted polyethylene (HXLPE) for TKAs. However, few in vivo comparative results of TKAs using HXLPE and less-crosslinked polyethylene inserts in the same patients are available, regarding fracture or failure of the locking mechanism of tibial polyethylene inserts or of osteolysis in patients younger than 60 years. We wanted to determine whether (1) survivorship free from aseptic loosening in knees with HXLPE inserts was different from survivorship in knees with less-crosslinked polyethylene inserts, (2) the prevalence of fracture or failure of the locking mechanism of the tibial polyethylene insert was greater in knees with HXLPE than in those with less-crosslinked polyethylene, and (3) the proportion of patients who had osteolysis develop was greater with HXLPE than with less-crosslinked polyethylene inserts. One hundred seventy-one patients with a mean age of 58 ± 8 years (range, 35-59 years) received posterior cruciate-retaining prostheses with a less-crosslinked polyethylene tibial insert in one knee and a HXLPE tibial insert in the contralateral knee. From January 2007 to January 2010, we performed 366 same-day bilateral simultaneous sequential posterior cruciate-retaining TKAs in 183 patients, of whom 171 (93%) participated in this study. All patients during this study period underwent posterior cruciate-retaining TKAs regardless of deformity of the knees and we did not perform posterior-stabilized TKAs during the same period. Patients who had bilateral end-stage osteoarthritis and were younger than 60 years were selected for inclusion. Six patients (4%) were lost to followup before 5 years. Twenty-six patients were males and 145 were females. The mean duration of followup was 6 years (range, 5-8 years). At each followup, patients were assessed for loosening of the components, fracture or failure of the locking mechanism of the polyethylene inserts, or osteolysis. The survival rate of the knee prosthesis at a mean of 5.8 years after surgery was 100% (95% CI, 0.95-1.00) in both groups for the endpoint aseptic loosening and 99.4% (95% CI, 0.95-1.00) in both groups for the endpoint revision. No knee in either group had fracture or failure of the locking mechanism of the tibial polyethylene insert, and none had osteolysis. With the numbers available, we found no clinically important differences between HXLPE and less-crosslinked polyethylene inserts in posterior cruciate-retaining TKAs. Given that HXLPE is newer, as-yet unproven, and more expensive than the proven technology (less-crosslinked polyethylene), we suggest not adopting HXLPE for clinical use until it shows superiority. Level I, therapeutic study.
Jaber, Sami Abdel; Merola, Massimiliano
2018-01-01
Given the long-term problem of polyethylene wear, medical interest in the new improved cross-linked polyethylene (XLPE), with or without the adding of vitamin E, has risen. The main aim of this study is to gain further insights into the mutual effects of radiation cross-linking and addition of vitamin E on the wear performance of ultra-high-molecular-weight polyethylene (UHMWPE). We tested four different batches of polyethylene (namely, a standard one, a vitamin E-stabilized, and two cross-linked) in a hip joint simulator for five million cycles where bovine calf serum was used as lubricant. The acetabular cups were then analyzed using a confocal profilometer to characterize the surface topography. Moreover; the cups were analyzed by using Fourier Transformed Infrared Spectroscopy and Differential Scanning Calorimetry in order to assess the chemical characteristics of the pristine materials. Comparing the different cups’ configuration, mass loss was found to be higher for standard polyethylene than for the other combinations. Mass loss negatively correlated to the cross-link density of the polyethylenes. None of the tested formulations showed evidence of oxidative degradation. We found no correlation between roughness parameters and wear. Furthermore, we found significantly differences in the wear behavior of all the acetabular cups. XLPEs exhibited lower weight loss, which has potential for reduced wear and decreased osteolysis. However, surface topography revealed smoother surfaces of the standard and vitamin E stabilized polyethylene than on the cross-linked samples. This observation suggests incipient crack generations on the rough and scratched surfaces of the cross-linked polyethylene liners. PMID:29547536
Cross-linked polyethylene does not reduce wear in total knee arthroplasty.
Lasurt-Bachs, S; Torner, P; Maculé, F; Prats, E; Menéndez-García, F; Ríos-Guillermo, J; Torrents, A
To compare two different types of inserts: Ultra-high molecular weight polyethylene (UHMWPE) and cross-linked polyethylene with a quantitative and qualitative study of polyethylene wear particles in synovial fluid 3 years after total knee arthroplasty. A prospective, randomized, controlled cohort study with blinded evaluation was carried out on 25 patients undergoing staged bilateral total knee replacement, 6 months apart. Knee arthrocentesis was performed on 12 patients 3 years after surgery, and the polyethylene particles were analyzed. No significant differences were found in the number of particles generated by the two different types of inserts at 3 years from total knee arthroplasty (3,000×: x¯ cross-linked=849.7; x¯ UHMWPE=796.9; P=.63; 20,000×: x¯ cross-linked=66.3; x¯ UHMWPE=73.1; P=.76). Likewise, no differences in the probability of finding elongated (χ 2 =0.19; P=.66) or rounded (χ 2 =1.44; P=.23) particles in both types of inserts were observed. However, the probability of finding fibrillar particles is 3.08 times greater in UHMWPE. Cross-linked polyethylene does not significantly reduce the generation of polyethylene particles in patients with total knee arthroplasty, 3 years after the surgical procedure. Copyright © 2018 SECOT. Publicado por Elsevier España, S.L.U. All rights reserved.
Yamamoto, Kengo; Masaoka, Toshinori; Manaka, Masakazu; Oonishi, Hironobu; Clarke, Ian; Shoji, Hiromu; Kawanabe, Keiichi; Imakiire, Atsuhiro
2004-04-01
We studied the micro-wear phenomena of unique, extensively cross-linked polyethylene cups (cross-linked with 1,000 kGy-irradiation) that had been used briefly in Japan. Two retrievals (at 15 years) came from the Japanese "SOM" hip system (implanted 1971-78). These were compared to a set of 0 kGy and 500-1,500 kGy cups run in our hip simulator. The polyethylene cups that had not been cross-linked had the greatest wear. The worn areas had a burnished appearance and were clearly separated from the unworn region by a distinct ridge-line. The worn areas had lost all machine tracks, showed a large amount of UHMWPE 'flow', and long PE fibrils. The associated surface rippling was degraded. These features were considered synonymous with severe polyethylene wear. In contrast, the worn areas in the very cross-linked cups had a visibly matte surface and no ridge-line. Micro-examination showed that the machine tracks were still present. Ripple formations were less obvious than in the cups that were not cross-linked, polyethylene surface fibrils were scarcer and all the fibrils were much smaller than in the cups that were not crosslinked. Our two retrieved cups and the simulator cups confirmed the greater wear-resistance of very cross-linked polyethylene. It should also be noted that the SOM cup design and processing were unique and differed greatly from that of modern polyethylene cups.
Thermal conductivity of cross-linked polyethylene from molecular dynamics simulation
NASA Astrophysics Data System (ADS)
Xiong, Xue; Yang, Ming; Liu, Changlin; Li, Xiaobo; Tang, Dawei
2017-07-01
The thermal conductivity of cross-linked bulk polyethylene is studied using molecular dynamics simulation. The atomic structure of the cross-linked polyethylene (PEX) is generated through simulated bond formation using LAMMPS. The thermal conductivity of PEX is studied with different degrees of crosslinking, chain length, and tensile strain. Generally, the thermal conductivity increases with the increasing degree of crosslinking. When the length of the primitive chain increases, the thermal conductivity increases linearly. When the polymer is stretched along one direction, the thermal conductivity increases in the stretched direction and decreases in the direction perpendicular to it. However, the thermal conductivity varies slightly when the polymer is stretched in three directions simultaneously.
In vivo oxidation in remelted highly cross-linked retrievals.
Currier, B H; Van Citters, D W; Currier, J H; Collier, J P
2010-10-20
Elimination of free radicals to prevent oxidation has played a major role in the development and product differentiation of the latest generation of highly cross-linked ultra-high molecular weight polyethylene bearing materials. In the current study, we (1) examined oxidation in a series of retrieved remelted highly cross-linked ultra-high molecular weight polyethylene bearings from a number of device manufacturers and (2) compared the retrieval results with findings for shelf-stored control specimens. The hypothesis was that radiation-cross-linked remelted ultra-high molecular weight polyethylene would maintain oxidative stability in vivo comparable with the stability during shelf storage and in published laboratory aging tests. Fifty remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners and nineteen remelted highly cross-linked ultra-high molecular weight polyethylene tibial inserts were received after retrieval from twenty-one surgeons from across the U.S. Thirty-two of the retrievals had been in vivo for two years or more. Each was measured for oxidation with use of Fourier transform infrared spectroscopy. A control series of remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners from three manufacturers was analyzed with electron paramagnetic resonance spectroscopy to measure free radical content and with Fourier transform infrared spectroscopy to measure oxidation initially and after eight to nine years of shelf storage in air. The never-implanted, shelf-aged controls had no measurable free-radical content initially or after eight to nine years of shelf storage. The never-implanted controls showed no increase in oxidation during shelf storage. Oxidation measurements showed measurable oxidation in 22% of the retrieved remelted highly cross-linked liners and inserts after an average of two years in vivo. Because never-implanted remelted highly cross-linked ultra-high molecular weight polyethylene materials had no measurable free-radical concentration and no increase in oxidation during shelf storage, these materials were expected to be oxidation-resistant in vivo. However, some remelted highly cross-linked ultra-high molecular weight polyethylene retrievals showed measurable oxidation after an average of more than two years in vivo. This apparent departure from widely expected behavior requires continued study of the process of in vivo oxidation of ultra-high molecular weight polyethylene materials.
Tribology of alternative bearings.
Fisher, John; Jin, Zhongmin; Tipper, Joanne; Stone, Martin; Ingham, Eileen
2006-12-01
The tribological performance and biological activity of the wear debris produced has been compared for highly cross-linked polyethylene, ceramic-on-ceramic, metal-on-metal, and modified metal bearings in a series of in vitro studies from a single laboratory. The functional lifetime demand of young and active patients is 10-fold greater than the estimated functional lifetime of traditional polyethylene. There is considerable interest in using larger diameter heads in these high demand patients. Highly cross-linked polyethylene show a four-fold reduction in functional biological activity. Ceramic-on-ceramic bearings have the lowest wear rates and least reactive wear debris. The functional biological activity is 20-fold lower than with highly cross-linked polyethylene. Hence, ceramic-on-ceramic bearings address the tribological lifetime demand of highly active patients. Metal-on-metal bearings have substantially lower wear rates than highly cross-linked polyethylene and wear decreases with head diameter. Bedding in wear is also lower with reduced radial clearance. Differential hardness ceramic-on-metal bearings and the application of ceramic-like coatings reduce metal wear and ion levels.
NASA Astrophysics Data System (ADS)
Teyssedre, G.; Vu, T. T. N.; Laurent, C.
2015-12-01
Among features observed in polyethylene materials under relatively high field, space charge packets, consisting in a pulse of net charge that remains in the form of a pulse as it crosses the insulation, are repeatedly observed but without complete theory explaining their formation and propagation. Positive charge packets are more often reported, and the models based on negative differential mobility(NDM) for the transport of holes could account for some charge packets phenomenology. Conversely, NDM for electrons transport has never been reported so far. The present contribution reports space charge measurements by pulsed electroacoustic method on miniature cables that are model of HVDC cables. The measurements were realized at room temperature or with a temperature gradient of 10 °C through the insulation under DC fields on the order 30-60 kV/mm. Space charge results reveal systematic occurrence of a negative front of charges generated at the inner electrode that moves toward the outer electrode at the beginning of the polarization step. It is observed that the transit time of the front of negative charge increases, and therefore the mobility decreases, with the applied voltage. Further, the estimated mobility, in the range 10-14-10-13 m2 V-1 s-1 for the present results, increases when the temperature increases for the same condition of applied voltage. The features substantiate the hypothesis of negative differential mobility used for modelling space charge packets.
Craig M. Clemons; Ronald C. Sabo; Kolby C. Hirth
2011-01-01
Though silane chemistry has been used to crosslink unfilled polyethylene for many years, such crosslinking has only been recently applied to wood plastic composites to improve properties such as creep resistance. However, the presence of wood significantly changes the silane chemistry and a greater understanding is necessary for optimal processing and performance. We...
Aging of XLPE cable insulation under combined electrical and mechanical stresses
DOE Office of Scientific and Technical Information (OSTI.GOV)
David, E.; Parpal, J.L.; Crine, J.P.
1996-12-31
Extruded crosslinked polyethylene (XLPE) insulation is widely used in high-voltage cables since it presents such attractive features as excellent dielectric properties and good thermomechanical behavior. However, its performance is affected by long-term degradation when it is subjected to the various thermal, mechanical and environmental stresses occurring in service in combination with electrical stress. The synergetic effect of superposed electrical and other stresses remains to be fully clarified. In particular, a fairly high level of mechanical stresses can be present in the insulation volume, originating from residual internal stresses created during the cooling process in the fabrication, external forces when cablesmore » are bent sharply, or thermomechanical stresses caused by differential thermal expansion between the conductor and the insulating material. In order to investigate the influence of the superposition of mechanical and electrical stresses, various measurements were conducted on XLPE and LDPE specimens in tip-plane and plane-plane geometries. Experimental data of time-to-breakdown, breakdown field and tree length are presented as a function of the magnitude of the stresses. In all cases, superposition of the mechanical stress was found to reduce the dielectric strength of the material.« less
Radiation cross-linking in ultra-high molecular weight polyethylene for orthopaedic applications
NASA Astrophysics Data System (ADS)
Oral, Ebru; Muratoglu, Orhun K.
2007-12-01
The motivation for radiation cross-linking of ultra-high molecular weight polyethylene (UHMWPE) is to increase its wear resistance to be used as bearing surfaces for total joint arthroplasty. However, radiation also leaves behind long-lived residual free radicals in this polymer, the reactions of which can detrimentally affect mechanical properties. In this review, we focus on the radiation cross-linking and oxidative stability of first and second generation highly cross-linked UHMWPEs developed in our laboratory.
NASA Astrophysics Data System (ADS)
Fu, Guopeng; Dempsey, Janel; Izaki, Kosuke; Adachi, Kaoru; Tsukahara, Yasuhisa; Kyu, Thein
2017-08-01
In an effort to fabricate highly conductive, stable solid-state polymer electrolyte membranes (PEM), polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction between polyethylene glycol diamine and ethylene carbonate. Subsequently, dimethacrylate groups were chemically attached to both ends of PEGBC to afford polyethylene glycol-bis-carbamate dimethacrylate (PEGBCDMA) precursor having crosslinking capability. The melt-mixed ternary mixtures consisting of PEGBCDMA, succinonitrile plasticizer, and lithium trifluorosulphonyl imide salt were completely miscible in a wide compositional range. Upon photo-crosslinking, the neat PEGBCDMA network was completely amorphous exhibiting higher tensile strength, modulus, and extensibility relative to polyethylene glycol diacrylate (PEGDA) counterpart. Likewise, the succinonitrile-plasticized PEM network containing PEGBCDMA remained completely amorphous and transparent upon photo-crosslinking, showing superionic conductivity, improved thermal stability, and superior tensile properties with improved capacity retention during charge/discharge cycling as compared to the PEGDA-based PEM.
40 CFR 721.7255 - Polyethyleneamine crosslinked with substituted polyethylene glycol (generic).
Code of Federal Regulations, 2010 CFR
2010-07-01
... PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.7255 Polyethyleneamine crosslinked with substituted polyethylene glycol (generic). (a) Chemical substance and significant new uses subject to...
NASA Astrophysics Data System (ADS)
Fan, Ching-Lin; Shang, Ming-Chi; Hsia, Mao-Yuan; Wang, Shea-Jue; Huang, Bohr-Ran; Lee, Win-Der
2016-03-01
A Microwave-Induction Heating (MIH) scheme is proposed for the poly(4-vinylphenol) (PVP) gate insulator cross-linking process to replace the traditional oven heating cross-linking process. The cross-linking time is significantly decreased from 1 h to 5 min by heating the metal below the PVP layer using microwave irradiation. The necessary microwave power was substantially reduced to about 50 W by decreasing the chamber pressure. The MIH scheme is a good candidate to replace traditional thermal heating for cross-linking of PVP as the gate insulator for organic thin-film-transistors.
Joyce, T J; Unsworth, A
1996-01-01
Wear tests were carried out on reciprocating pin-on-plate machines which had pins loaded at 10 N and 40 N. The materials tested were irradiated cross-linked polyethylene sliding against itself, irradiated ultra-high molecular weight polyethylene sliding against itself and non-irradiated ultra-high molecular weight polyethylene sliding against itself. After 153.5 km of sliding, the non-irradiated ultra-high molecular weight polyethylene plates and pins showed mean wear factors under 10 N loads, or a nominal contact stress of 0.51 MPa, of 84.0 x 10(-6) mm3/N m for the plates and 81.3 x 10(-6) mm3/N m for the pins. Under 40 N loads, or a nominal contact stress of 2.04 MPa, the non-irradiated ultra-high molecular weight polyethylene pins sheared at 22.3 km. At the last measurement point prior to this failure, 19.1 km, wear factors of 158 x 10(-6) mm3/N m for the plates and 85.0 x 10(-6) mm3/N m for the pins had been measured. After 152.8 km. the irradiated ultra-high molecular weight polyethylene plates and pins showed mean wear factors under 10 N loads of 59.8 x 10(-6) mm3/N m for the plates and 31.1 x 10(-6) mm3/N m for the pins. In contrast, after 150.2 km, a mean wear factor of 0.72 x 10(-6) mm3/N m was found for the irradiated cross-linked polyethylene plates compared with 0.053 x 10(-6) mm3/N m for the irradiated cross-linked polyethylene pins.
Enhanced wear performance of ultra high molecular weight polyethylene crosslinked by organosilane.
Tang, C Y; Xie, X L; Wu, X C; Li, R K Y; Mai, Y W
2002-11-01
Ultra high molecular weight polyethylene (UHMWPE) crosslinked by organosilane was thermal compression molded. The organosilane used was the tri-ethyloxyl vinyl silane. Its gelation, melting behavior, crystallinity, mechanical and wear-resisting properties were systematically investigated. The results showed that the gel ratio of UHMWPE increases with the incorporation of organosilane. At a low content of organosilane, the melting point and crystallinity of the crosslinked UHMWPE increase, and hence the mechanical and wear-resisting properties are improved. However, at a high content of organosilane, these performances of the crosslinked UHMWPE become worse. At 0.4 phr silane, the wear resistance of crosslinked UHMWPE reaches its optimum value.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bradley, J.M.
The feasibility of building a freeze-tolerant absorber for a solar water heater out of carbon-black-reinforced crosslinked polyethylene has been explored. Ten-foot tube specimens made from various crosslinked polyethylene formulations were filled with water at various pressures, and then placed into a deep freeze, then thawed and frozen again for 100 freeze-thaw cycles, or until the tube specimen failed. Tube diameters were measured before and after each freezing to determine how much distention the freezing caused, and how much permanent distention was caused by the strains of repeated freezings. Five tube specimens containing water at as high as 80 psi survivedmore » 100 freeze-thaw cycles. Also, a flat plate collector was fabricated using as absorber surface a single 400 ft tube of carbon-black-reinforced crosslinked polyethylene in the form of a flat spiral coil and this collector was tested for performance at the Los Alamos Scientific Laboratory. The performance test indicates that the absorbancy of such a flat spiral coil to solar radiation is similar to typical black surfaces used on solar absorbers. Thus, it does seem very feasible that domestic water can be directly heated in a solar collector having an absorber made from crosslinked polyethylene, and that this collector can safely withstand at least 100 freeze-thaw cycles.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Teyssedre, G., E-mail: gilbert.teyssedre@laplace.univ-tlse.fr; Laurent, C.; CNRS, LAPLACE, F-31062 Toulouse
Among features observed in polyethylene materials under relatively high field, space charge packets, consisting in a pulse of net charge that remains in the form of a pulse as it crosses the insulation, are repeatedly observed but without complete theory explaining their formation and propagation. Positive charge packets are more often reported, and the models based on negative differential mobility(NDM) for the transport of holes could account for some charge packets phenomenology. Conversely, NDM for electrons transport has never been reported so far. The present contribution reports space charge measurements by pulsed electroacoustic method on miniature cables that are modelmore » of HVDC cables. The measurements were realized at room temperature or with a temperature gradient of 10 °C through the insulation under DC fields on the order 30–60 kV/mm. Space charge results reveal systematic occurrence of a negative front of charges generated at the inner electrode that moves toward the outer electrode at the beginning of the polarization step. It is observed that the transit time of the front of negative charge increases, and therefore the mobility decreases, with the applied voltage. Further, the estimated mobility, in the range 10{sup −14}–10{sup −13} m{sup 2} V{sup −1} s{sup −1} for the present results, increases when the temperature increases for the same condition of applied voltage. The features substantiate the hypothesis of negative differential mobility used for modelling space charge packets.« less
Applications of fibrous substrates containing insolubilized phase change polymers
NASA Technical Reports Server (NTRS)
Vigo, Tyrone L.; Bruno, Joseph S.
1993-01-01
Incorporation of polyethylene glycols into fibrous substrates produces several improved functional properties when they are insolubilized by crosslinking with a methylolamide resin or by polyacetal formation by their reaction with glyoxal. The range of molecular weights of polyols that may be insolubilized is broad as are the curing conditions (0.25-10 min at 80-200C). Most representative fiber types and blends (natural and synthetic) and all types of fabric constructions (woven, nonwoven and knit) have been modified by incorporation of the bound polyols. The most novel property is the thermal adaptability of the modified substrates to many climatic conditions. This adaptability is due to the high latent heat of the crosslinked polyols that function as phase change materials, the hydrophilic nature of the crosslinked polymer and its enhanced thermal conductivity. Other enhanced properties imparted to fabrics include flex and flat abrasion, antimicrobial activity, reduced static charge, resistance to oily soils, resiliency, wind resistance and reduced lint loss. Applications commercialized in the U.S. and Japan include sportswear and skiwear. Several examples of electric sets of properties useful for specific end uses are given. In addition, other uses are biomedical horticultural, aerospace, indoor insulation, automotive interiors and components and packaging material.
Applications of fibrous substrates containing insolubilized phase change polymers
NASA Astrophysics Data System (ADS)
Vigo, Tyrone L.; Bruno, Joseph S.
1993-02-01
Incorporation of polyethylene glycols into fibrous substrates produces several improved functional properties when they are insolubilized by crosslinking with a methylolamide resin or by polyacetal formation by their reaction with glyoxal. The range of molecular weights of polyols that may be insolubilized is broad as are the curing conditions (0.25-10 min at 80-200C). Most representative fiber types and blends (natural and synthetic) and all types of fabric constructions (woven, nonwoven and knit) have been modified by incorporation of the bound polyols. The most novel property is the thermal adaptability of the modified substrates to many climatic conditions. This adaptability is due to the high latent heat of the crosslinked polyols that function as phase change materials, the hydrophilic nature of the crosslinked polymer and its enhanced thermal conductivity. Other enhanced properties imparted to fabrics include flex and flat abrasion, antimicrobial activity, reduced static charge, resistance to oily soils, resiliency, wind resistance and reduced lint loss. Applications commercialized in the U.S. and Japan include sportswear and skiwear. Several examples of electric sets of properties useful for specific end uses are given. In addition, other uses are biomedical horticultural, aerospace, indoor insulation, automotive interiors and components and packaging material.
Zanini, Filippo; Carmignato, Simone
2017-01-01
More than 60.000 hip arthroplasty are performed every year in Italy. Although Ultra-High-Molecular-Weight-Polyethylene remains the most used material as acetabular cup, wear of this material induces over time in vivo a foreign-body response and consequently osteolysis, pain, and the need of implant revision. Furthermore, oxidative wear of the polyethylene provoke several and severe failures. To solve these problems, highly cross-linked polyethylene and Vitamin-E-stabilized polyethylene were introduced in the last years. In in vitro experiments, various efforts have been made to compare the wear behavior of standard PE and vitamin-E infused liners. In this study we compared the in vitro wear behavior of two different configurations of cross-linked polyethylene (with and without the add of Vitamin E) vs. the standard polyethylene acetabular cups. The aim of the present study was to validate a micro X-ray computed tomography technique to assess the wear of different commercially available, polyethylene’s acetabular cups after wear simulation; in particular, the gravimetric method was used to provide reference wear values. The agreement between the two methods is documented in this paper. PMID:28107468
First-principle simulations of electronic structure in semicrystalline polyethylene
NASA Astrophysics Data System (ADS)
Moyassari, A.; Unge, M.; Hedenqvist, M. S.; Gedde, U. W.; Nilsson, F.
2017-05-01
In order to increase our fundamental knowledge about high-voltage cable insulation materials, realistic polyethylene (PE) structures, generated with a novel molecular modeling strategy, have been analyzed using first principle electronic structure simulations. The PE structures were constructed by first generating atomistic PE configurations with an off-lattice Monte Carlo method and then equilibrating the structures at the desired temperature and pressure using molecular dynamics simulations. Semicrystalline, fully crystalline and fully amorphous PE, in some cases including crosslinks and short-chain branches, were analyzed. The modeled PE had a structure in agreement with established experimental data. Linear-scaling density functional theory (LS-DFT) was used to examine the electronic structure (e.g., spatial distribution of molecular orbitals, bandgaps and mobility edges) on all the materials, whereas conventional DFT was used to validate the LS-DFT results on small systems. When hybrid functionals were used, the simulated bandgaps were close to the experimental values. The localization of valence and conduction band states was demonstrated. The localized states in the conduction band were primarily found in the free volume (result of gauche conformations) present in the amorphous regions. For branched and crosslinked structures, the localized electronic states closest to the valence band edge were positioned at branches and crosslinks, respectively. At 0 K, the activation energy for transport was lower for holes than for electrons. However, at room temperature, the effective activation energy was very low (˜0.1 eV) for both holes and electrons, which indicates that the mobility will be relatively high even below the mobility edges and suggests that charge carriers can be hot carriers above the mobility edges in the presence of a high electrical field.
Classification of Partial Discharge Measured under Different Levels of Noise Contamination.
Jee Keen Raymond, Wong; Illias, Hazlee Azil; Abu Bakar, Ab Halim
2017-01-01
Cable joint insulation breakdown may cause a huge loss to power companies. Therefore, it is vital to diagnose the insulation quality to detect early signs of insulation failure. It is well known that there is a correlation between Partial discharge (PD) and the insulation quality. Although many works have been done on PD pattern recognition, it is usually performed in a noise free environment. Also, works on PD pattern recognition in actual cable joint are less likely to be found in literature. Therefore, in this work, classifications of actual cable joint defect types from partial discharge data contaminated by noise were performed. Five cross-linked polyethylene (XLPE) cable joints with artificially created defects were prepared based on the defects commonly encountered on site. Three different types of input feature were extracted from the PD pattern under artificially created noisy environment. These include statistical features, fractal features and principal component analysis (PCA) features. These input features were used to train the classifiers to classify each PD defect types. Classifications were performed using three different artificial intelligence classifiers, which include Artificial Neural Networks (ANN), Adaptive Neuro-Fuzzy Inference System (ANFIS) and Support Vector Machine (SVM). It was found that the classification accuracy decreases with higher noise level but PCA features used in SVM and ANN showed the strongest tolerance against noise contamination.
Influence of thermal aging on AC leakage current in XLPE insulation
NASA Astrophysics Data System (ADS)
Geng, Pulong; Song, Jiancheng; Tian, Muqin; Lei, Zhipeng; Du, Yakun
2018-02-01
Cross-linked polyethylene (XLPE) has been widely used as cable insulation material because of its excellent dielectric properties, thermal stability and solvent resistance. To understand the influence of thermal aging on AC leakage current in XLPE insulation, all XLPE specimens were aged in oven in temperature range from 120 °C to 150 °C, and a series of tests were conducted on these XLPE specimens in different aging stages to measure the characteristic parameters, such as complex permittivity, leakage current and complex dielectric modulus. In the experiments, the effects of thermal aging, temperature and frequency on the AC leakage current in XLPE insulation were studied by analyzing complex dielectric constant and dielectric relaxation modulus spectrum, the change of relaxation peak and activation energy. It has been found that the active part of leakage current increases sharply with the increase of aging degree, and the test temperature and frequency have an influence on AC leakage current but the influence of test temperature is mainly reflected in the low frequency region. In addition, it has been shown by the experiments that the reactive part of leakage current exhibits a strong frequency dependent characteristic in the testing frequency range from 10-2 Hz to 105 Hz, but the influence of test temperature and thermal aging on it is relatively small.
NASA Astrophysics Data System (ADS)
Lu, Canhui; Zhang, Xinxing; Zhang, Wei
2015-05-01
The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. The results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.
Nakahara, Ichiro; Nakamura, Nobuo; Nishii, Takashi; Miki, Hidenobu; Sakai, Takashi; Sugano, Nobuhiko
2010-12-01
We investigated the efficacy of combining highly cross-linked polyethylene with ceramic heads on further reduction in polyethylene wear compared with the combination with cobalt-chromium heads via PolyWare computer-assisted method. A prospective cohort study was performed on 102 cementless total hip arthroplasties using Longevity (Zimmer, Warsaw, Ind) highly cross-linked polyethylene liners. Either 26-mm zirconia heads or 26-mm cobalt-chromium heads were randomly used in 51 hips each. At a mean follow-up of 6.7 years, no significant differences were identified between the groups for total penetration rate and steady-state wear rate. Osteolysis was not observed in any hips in either group. In conclusion, no advantage was seen for the 26-mm zirconia head compared with the 26-mm cobalt-chromium head in this period. Copyright © 2010 Elsevier Inc. All rights reserved.
Abdelgaied, Abdellatif; Brockett, Claire L; Liu, Feng; Jennings, Louise M; Fisher, John; Jin, Zhongmin
2013-01-01
Polyethylene wear is a great concern in total joint replacement. It is now considered a major limiting factor to the long life of such prostheses. Cross-linking has been introduced to reduce the wear of ultra-high-molecular-weight polyethylene (UHMWPE). Computational models have been used extensively for wear prediction and optimization of artificial knee designs. However, in order to be independent and have general applicability and predictability, computational wear models should be based on inputs from independent experimentally determined wear parameters (wear factors or wear coefficients). The objective of this study was to investigate moderately cross-linked UHMWPE, using a multidirectional pin-on-plate wear test machine, under a wide range of applied nominal contact pressure (from 1 to 11 MPa) and under five different kinematic inputs, varying from a purely linear track to a maximum rotation of +/- 55 degrees. A computational model, based on a direct simulation of the multidirectional pin-on-plate wear tester, was developed to quantify the degree of cross-shear (CS) of the polyethylene pins articulating against the metallic plates. The moderately cross-linked UHMWPE showed wear factors less than half of that reported in the literature for, the conventional UHMWPE, under the same loading and kinematic inputs. In addition, under high applied nominal contact stress, the moderately crosslinked UHMWPE wear showed lower dependence on the degree of CS compared to that under low applied nominal contact stress. The calculated wear coefficients were found to be independent of the applied nominal contact stress, in contrast to the wear factors that were shown to be highly pressure dependent. This study provided independent wear data for inputs into computational models for moderately cross-linked polyethylene and supported the application of wear coefficient-based computational wear models.
Gas-phase transfer of polymer cross-linking agents and by-products to solid oral pharmaceuticals.
Maus, Russell G; Li, Min; Clement, Christopher M; Kinzer, Jeffery A
2007-11-05
In the pharmaceutical industry, solid oral compressed tablets (OCT) are frequently transported in bulk containers prior to packaging. While in this state, the product is generally protected from interaction with liquid and solid contaminants by physical barriers (e.g., polyethylene bags, drums, etc.). Vapor phase contamination, although generally less frequently observed, is possible. A specific example of the detection and identification of volatile by-products (acetophenone and 2-phenyl-2-propanol) of a common polymer cross-linking agent (dicumyl peroxide) is presented. The product tablets were compressed, placed into double polyethylene bags, and subsequently placed into a polyethylene drum for shipment overseas. To cushion the product during transit, a cross-linked polyethylene foam disk (designed to fit into the bottom of the drum) was placed below the bag of tablets. Initially, these contaminants were detected by HPLC with UV detection at the receiving laboratory, and assumed to be degradates of the active components of the product. Further analysis showed that neither the collected UV absorbance data nor the observed levels of the contaminants were consistent with known degradates of the product. Liquid extraction followed by GC-MS analysis of the product as well as the cross-linked foam disk exhibited measurable quantities of the contaminants in question. Vapor phase transfer of these cross-linking agent by-products, originating in the cross-linked foam pads, was determined to be the root cause for the presence of these compounds in the product.
Tribological characterisation of UHMWPE used in dual mobility total hip prosthesis
NASA Astrophysics Data System (ADS)
Essefi, I.; Hakkouna, H.; Ouenzerfi, G.; Mollon, G.; Hamza, S.; Renault, E.; Berthier, Y.; Trunfio-Sfarghiu, A.-M.
2016-08-01
Total hip arthroplasty represents an effective solution for bone and joint diseases. Nevertheless, the hip prosthesis has a limited lifetime, in the average around fifteen years. Their improvement, especially their dual mobility is the objective of this study. Therefore, our strategy is focused on improving the material by comparing three types of polyethylene to determine the best one from a friction mechanism and wear rate minimization standpoint. A dual mobility hip prosthesis, containing a two-sided steel and cobalt chrome cup, was tested with a TORNIER hip joint simulator in calf serum. The rubbed surfaces were characterized using scanning electron microscopy (SEM), contact angle measurements, atomic force microscopy (AFM) and confocal fluorescence microscopy. All these multiscale characterization techniques (from nanoscale to millimeter and micro- scale) showed that the velocity accommodation mechanism is different from one type of polyethylene to another. The wear in the case of standard polyethylene was noticeable and the particles were large and scattered between the surface of polyethylene, the surface of the cup and in the calf serum. For the crosslinked polyethylene, the particles coming from the wear, were not as large, but they were spread the same way as the first case. Even though it shares the same accommodation principle on the detachment of the material with the crosslinked polyethylene the wear particles for the crosslinked vitaminized polyethylene were large and they were only found on the surface of the polyethylene.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lu, Canhui; Zhang, Xinxing; Zhang, Wei
The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. Themore » results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.« less
Durability and mechanical properties of silane cross-linked wood thermoplastic composites
Magnus Bengtsson; Nicole M. Stark; Kristiina Oksman
2007-01-01
In this study, silane cross-linked woodâpolyethylene composite profiles were manufactured by reactive extrusion. These composites were evaluated regarding their durability and mechanical properties in comparison with two non-cross-linked woodâ polyethylene composites. An addition of only 2% w/w of silane solution during manufacturing was enough to achieve almost 60%...
Wear versus Thickness and Other Features of 5-Mrad Crosslinked UHMWPE Acetabular Liners
Shen, Fu-Wen; Lu, Zhen
2010-01-01
Background The low wear rates of crosslinked polyethylenes provide the potential to use larger diameters to resist dislocation. However, this requires the use of thinner liners in the acetabular component, with concern that higher contact stresses will increase wear, offsetting the benefits of the crosslinking. Questions/purposes We asked the following questions: Is the wear of conventional and crosslinked polyethylene liners affected by ball diameter, rigidity of backing, and liner thickness? Are the stresses in the liner affected by thickness? Methods Wear rates were measured in a hip simulator and stresses were calculated using finite element modeling. Results Without crosslinking, the wear rate was 4% to 10% greater with a 36-mm diameter than a 28-mm diameter. With crosslinking, wear was 9% lower with a 36-mm diameter without metal backing and 4% greater with metal backing. Reducing the thickness from 6 mm to 3 mm increased the contact stress by 46%, but the wear rate decreased by 19%. Conclusions The reduction in wear with 5 Mrad of crosslinking was not offset by increasing the diameter from 28 mm to 36 mm or by using a liner as thin as 3 mm. Clinical Relevance The results indicate, for a properly positioned 5-Mrad crosslinked acetabular component and within the range of dimensions evaluated, neither wear nor stresses in the polyethylene are limiting factors in the use of larger-diameter, thinner cups to resist dislocation. PMID:20848244
Structural Composite Construction Materials Manufactured from Municipal Solid Waste
1994-04-20
in Table 1. Candidate matrix materials included polystyrene (PS) or expanded polystyrene (EPS), high density polyethylene (HDPE), and polyethylene...companies make a variety of expanded polystyrene insulation panels that arc used in insulation and roofing systems.46 Thermoplastics are seeing
Classification of Partial Discharge Measured under Different Levels of Noise Contamination
2017-01-01
Cable joint insulation breakdown may cause a huge loss to power companies. Therefore, it is vital to diagnose the insulation quality to detect early signs of insulation failure. It is well known that there is a correlation between Partial discharge (PD) and the insulation quality. Although many works have been done on PD pattern recognition, it is usually performed in a noise free environment. Also, works on PD pattern recognition in actual cable joint are less likely to be found in literature. Therefore, in this work, classifications of actual cable joint defect types from partial discharge data contaminated by noise were performed. Five cross-linked polyethylene (XLPE) cable joints with artificially created defects were prepared based on the defects commonly encountered on site. Three different types of input feature were extracted from the PD pattern under artificially created noisy environment. These include statistical features, fractal features and principal component analysis (PCA) features. These input features were used to train the classifiers to classify each PD defect types. Classifications were performed using three different artificial intelligence classifiers, which include Artificial Neural Networks (ANN), Adaptive Neuro-Fuzzy Inference System (ANFIS) and Support Vector Machine (SVM). It was found that the classification accuracy decreases with higher noise level but PCA features used in SVM and ANN showed the strongest tolerance against noise contamination. PMID:28085953
Kawate, Kenji; Ohmura, Tetsuji; Kawahara, Ikuo; Tamai, Katsuya; Ueha, Tomoyuki; Takemura, Kazuo
2009-12-01
The purpose of this study was to compare highly cross-linked polyethylene wear between the zirconia head and the cobalt-chromium head in Japanese patients. A prospective, randomized study was performed to evaluate the outcomes in 32 hips that had zirconia heads and in 30 hips that had cobalt-chromium heads. The mean follow-up periods of both groups were same (5 years). There were no significant differences between the zirconia head and the cobalt-chromium head in the mean polyethylene linear wear per year and the mean volumetric polyethylene wear per year in the steady phase. This study indicates that zirconia head offers no benefits over metal head in terms of wear reduction at 5 years in Japanese patients who have lightweight and thin polyethylene liners.
Carter, B H; Friend, T H; Garey, S M; Sawyer, J A; Alexander, M B; Tomazewski, M A
2014-01-01
The objective of this study was to determine the ability of radiant insulation hutch covers to moderate the effect of ambient temperature and radiant energy on calves housed in polyethylene hutches. The insulation had a double layer of polyethylene bubble film laminated between a layer of aluminum foil and white polyethylene (reflectance = 95%, R value (ft(2) · °F ·h/Btu) = 2.7). In each of two experiments (exp.), hutches were either uninsulated (control) or covered with reflective insulation across the top and sides of the hutch leaving the front, back, and pen exposed. Each hutch had a 1.2 × 1.8-m attached outdoor wire pen. In both exp., rate of increase of interior hutch temperature relative to ambient temperature was lower in insulated hutches (P < 0.001) indicating they were warmer at low THI and cooler at high THI. In exp. 1, increase in respiration rate and ear canal temperature of the calves, relative to THI, were moderated in insulated hutches (P < 0.001). In Exp. 2, respiration rate was not affected by treatment (P = 0.50), but increased with increasing THI (P < 0.001). Mean ADG did not differ among treatments in either exp. (P > 0.21). Insulating calf hutches with reflective insulation moderated hutch microclimate, and improved calf comfort, but did not translate to improvements in economically relevant variables such as ADG.
Development of radiation resistant electrical cable insulations
NASA Technical Reports Server (NTRS)
Lee, B. S.; Soo, P.; Mackenzie, D. R.
1994-01-01
Two new polyethylene cable insulations have been formulated for nuclear applications and have been tested under gamma radiation. Both insulations are based on low density polyethylene, one with PbO and the other with Sb2O3 as additives. The test results show that the concept of using inorganic antioxidants to retard radiation initiated oxidation (RIO) is viable. PbO is more effective than Sb2O3 in minimizing RIO.
Song, Shuwei; Zhao, Hong; Zheng, Xiaonan; Zhang, Hui; Wang, Ying; Han, Baozhong
2018-01-01
The role of a series of functionalized graphene additives in power cable insulation in suppressing the growth of electrical treeing and preventing the degradation of the polymer matrix has been investigated by density functional theory calculations. Bader charge analysis indicates that pristine, doped or defect graphene could effectively capture hot electrons to block their attack on cross-linked polyethylene (XLPE) because of the π–π conjugated unsaturated structures. Further exploration of the electronic properties in the interfacial region between the additives and XLPE shows that N-doped single-vacancy graphene, graphene oxide and B-, N-, Si- or P-doped graphene oxide have relatively strong physical interaction with XLPE to restrict its mobility and rather weak chemical activity to prevent the cleavage of the C–H or C–C bond, suggesting that they are all potential candidates as effective additives. The understanding of the features of functionalized graphene additives in trapping electrons and interfacial interaction will assist in the screening of promising additives as voltage stabilizers in power cables. PMID:29515821
Song, Shuwei; Zhao, Hong; Zheng, Xiaonan; Zhang, Hui; Liu, Yang; Wang, Ying; Han, Baozhong
2018-02-01
The role of a series of functionalized graphene additives in power cable insulation in suppressing the growth of electrical treeing and preventing the degradation of the polymer matrix has been investigated by density functional theory calculations. Bader charge analysis indicates that pristine, doped or defect graphene could effectively capture hot electrons to block their attack on cross-linked polyethylene (XLPE) because of the π-π conjugated unsaturated structures. Further exploration of the electronic properties in the interfacial region between the additives and XLPE shows that N-doped single-vacancy graphene, graphene oxide and B-, N-, Si- or P-doped graphene oxide have relatively strong physical interaction with XLPE to restrict its mobility and rather weak chemical activity to prevent the cleavage of the C-H or C-C bond, suggesting that they are all potential candidates as effective additives. The understanding of the features of functionalized graphene additives in trapping electrons and interfacial interaction will assist in the screening of promising additives as voltage stabilizers in power cables.
Affatato, Saverio; De Mattia, Jonathan Salvatore; Bracco, Pierangiola; Pavoni, Eleonora; Taddei, Paola
2016-06-01
First-generation (irradiated and remelted or annealed) and second-generation (irradiated and vitamin E blended or doped) highly crosslinked polyethylenes were introduced in the last decade to solve the problems of wear and osteolysis. In this study, the influence of the Vitamin-E addition on crosslinked polyethylene (XLPE_VE) was evaluated by comparing the in vitro wear behavior of crosslinked polyethylene (XLPE) versus Vitamin-E blended polyethylene XLPE and conventional ultra-high molecular weight polyethylene (STD_PE) acetabular cups, after accelerated ageing according to ASTM F2003-02 (70.0±0.1°C, pure oxygen at 5bar for 14 days). The test was performed using a hip joint simulator run for two millions cycles, under bovine calf serum as lubricant. Mass loss was found to decrease along the series XLPE_VE>STD_PE>XLPE, although no statistically significant differences were found between the mass losses of the three sets of cups. Micro-Raman spectroscopy was used to investigate at a molecular level the morphology changes induced by wear. The spectroscopic analyses showed that the accelerated ageing determined different wear mechanisms and molecular rearrangements during testing with regards to the changes in both the chain orientation and the distribution of the all-trans sequences within the orthorhombic, amorphous and third phases. The results of the present study showed that the addition of vitamin E was not effective to improve the gravimetric wear of PE after accelerated ageing. However, from a molecular point of view, the XLPE_VE acetabular cups tested after accelerated ageing appeared definitely less damaged than the STD_PE ones and comparable to XLPE samples. Copyright © 2016 Elsevier Ltd. All rights reserved.
Wear Analysis in THA Utilizing Oxidized Zirconium and Crosslinked Polyethylene
Garvin, Kevin L.; Mangla, Jimmi; Murdoch, Nathan; Martell, John M.
2008-01-01
Oxidized zirconium, a material with a ceramic surface on a metal substrate, and highly cross-linked polyethylene are two materials developed to reduce wear. We measured in vivo femoral head penetration in patients with these advanced bearings. We hypothesized the linear wear rates would be lower than those published for cobalt-chrome and standard polyethylene. We retrospectively reviewed a select series of 56 THAs in a relatively young, active patient population utilizing oxidized zirconium femoral heads and highly cross-linked polyethylene acetabular liners. Femoral head penetration was determined using the Martell computerized edge-detection method. All patients were available for 2-year clinical and radiographic followup. True linear wear was 4 μm/year (95% confidence intervals, ± 59 μm/year). The early wear rates in this cohort of relatively young, active patients were low and we believe justify the continued study of these alternative bearing surfaces. Level of Evidence: Level IV, therapeutic study. See the Guidelines for Authors for a complete description of levels of evidence. PMID:18946711
Fan, Ching-Lin; Shang, Ming-Chi; Wang, Shea-Jue; Hsia, Mao-Yuan; Lee, Win-Der; Huang, Bohr-Ran
2017-01-01
In this study, a proposed Microwave-Induction Heating (MIH) scheme has been systematically studied to acquire suitable MIH parameters including chamber pressure, microwave power and heating time. The proposed MIH means that the thin indium tin oxide (ITO) metal below the Poly(4-vinylphenol) (PVP) film is heated rapidly by microwave irradiation and the heated ITO metal gate can heat the PVP gate insulator, resulting in PVP cross-linking. It is found that the attenuation of the microwave energy decreases with the decreasing chamber pressure. The optimal conditions are a power of 50 W, a heating time of 5 min, and a chamber pressure of 20 mTorr. When suitable MIH parameters were used, the effect of PVP cross-linking and the device performance were similar to those obtained using traditional oven heating, even though the cross-linking time was significantly decreased from 1 h to 5 min. Besides the gate leakage current, the interface trap state density (Nit) was also calculated to describe the interface status between the gate insulator and the active layer. The lowest interface trap state density can be found in the device with the PVP gate insulator cross-linked by using the optimal MIH condition. Therefore, it is believed that the MIH scheme is a good candidate to cross-link the PVP gate insulator for organic thin-film transistor applications as a result of its features of rapid heating (5 min) and low-power microwave-irradiation (50 W). PMID:28773101
Fan, Ching-Lin; Shang, Ming-Chi; Wang, Shea-Jue; Hsia, Mao-Yuan; Lee, Win-Der; Huang, Bohr-Ran
2017-07-03
In this study, a proposed Microwave-Induction Heating (MIH) scheme has been systematically studied to acquire suitable MIH parameters including chamber pressure, microwave power and heating time. The proposed MIH means that the thin indium tin oxide (ITO) metal below the Poly(4-vinylphenol) (PVP) film is heated rapidly by microwave irradiation and the heated ITO metal gate can heat the PVP gate insulator, resulting in PVP cross-linking. It is found that the attenuation of the microwave energy decreases with the decreasing chamber pressure. The optimal conditions are a power of 50 W, a heating time of 5 min, and a chamber pressure of 20 mTorr. When suitable MIH parameters were used, the effect of PVP cross-linking and the device performance were similar to those obtained using traditional oven heating, even though the cross-linking time was significantly decreased from 1 h to 5 min. Besides the gate leakage current, the interface trap state density (Nit) was also calculated to describe the interface status between the gate insulator and the active layer. The lowest interface trap state density can be found in the device with the PVP gate insulator cross-linked by using the optimal MIH condition. Therefore, it is believed that the MIH scheme is a good candidate to cross-link the PVP gate insulator for organic thin-film transistor applications as a result of its features of rapid heating (5 min) and low-power microwave-irradiation (50 W).
Bin Imran, Abu; Esaki, Kenta; Gotoh, Hiroaki; Seki, Takahiro; Ito, Kohzo; Sakai, Yasuhiro; Takeoka, Yukikazu
2014-10-08
Stimuli-sensitive hydrogels changing their volumes and shapes in response to various stimulations have potential applications in multiple fields. However, these hydrogels have not yet been commercialized due to some problems that need to be overcome. One of the most significant problems is that conventional stimuli-sensitive hydrogels are usually brittle. Here we prepare extremely stretchable thermosensitive hydrogels with good toughness by using polyrotaxane derivatives composed of α-cyclodextrin and polyethylene glycol as cross-linkers and introducing ionic groups into the polymer network. The ionic groups help the polyrotaxane cross-linkers to become well extended in the polymer network. The resulting hydrogels are surprisingly stretchable and tough because the cross-linked α-cyclodextrin molecules can move along the polyethylene glycol chains. In addition, the polyrotaxane cross-linkers can be used with a variety of vinyl monomers; the mechanical properties of the wide variety of polymer gels can be improved by using these cross-linkers.
Bin Imran, Abu; Esaki, Kenta; Gotoh, Hiroaki; Seki, Takahiro; Ito, Kohzo; Sakai, Yasuhiro; Takeoka, Yukikazu
2014-01-01
Stimuli-sensitive hydrogels changing their volumes and shapes in response to various stimulations have potential applications in multiple fields. However, these hydrogels have not yet been commercialized due to some problems that need to be overcome. One of the most significant problems is that conventional stimuli-sensitive hydrogels are usually brittle. Here we prepare extremely stretchable thermosensitive hydrogels with good toughness by using polyrotaxane derivatives composed of α-cyclodextrin and polyethylene glycol as cross-linkers and introducing ionic groups into the polymer network. The ionic groups help the polyrotaxane cross-linkers to become well extended in the polymer network. The resulting hydrogels are surprisingly stretchable and tough because the cross-linked α-cyclodextrin molecules can move along the polyethylene glycol chains. In addition, the polyrotaxane cross-linkers can be used with a variety of vinyl monomers; the mechanical properties of the wide variety of polymer gels can be improved by using these cross-linkers. PMID:25296246
NASA Astrophysics Data System (ADS)
Yang, Chenguang; Xing, Zhe; Zhang, Mingxing; Zhao, Quan; Wang, Mouhua; Wu, Guozhong
2017-12-01
A blend of isotactic polypropylene (PP) with high-density polyethylene (HDPE) in different PP/HDPE ratios was irradiated by γ-ray to induce cross-linking and then foamed using supercritical carbon dioxide (scCO2) as a blowing agent. Radiation effect on the melting point and crystallinity were analyzed in detail. The average cell diameter and cell density were compared for PP/HDPE foams prepared under different conditions. The optimum absorbed dose for the scCO2 foaming of PP/HDPE in terms of foaming ability and cell structure was 20 kGy. Tensile measurements showed that the elongation at break and tensile strength at break of the crosslinked PP/HDPE foams were higher than the non-crosslinked ones. Of particular interest was the increase in the foaming temperature window from 4 ℃ for pristine PP to 8-12 ℃ for the radiation crosslinked PP/HDPE blends. This implies much easier handling of scCO2 foaming of crosslinked PP with the addition of HDPE.
Ion conducting polymers and polymer blends for alkali metal ion batteries
DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra
2017-08-29
Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.
Hydrogels Prepared from Cross-Linked Nanofibrillated Cellulose
Sandeep S. Nair; J.Y. Zhu; Yulin Deng; Arthur J. Ragauskas
2014-01-01
Nanocomposite hydrogels were developed by cross-linking nanofibrillated cellulose with poly(methyl vinyl ether-co-maleic acid) and polyethylene glycol. The cross-linked hydrogels showed enhanced water absorption and gel content with the addition of nanocellulose. In addition, the thermal stability, mechanical strength, and modulus increased with an increase in the...
Self-Healable Electrical Insulation for High Voltage Applications
NASA Technical Reports Server (NTRS)
Williams, Tiffany S.
2017-01-01
Polymeric aircraft electrical insulation normally degrades by partial discharge with increasing voltage, which causes excessive localized Joule heating in the material and ultimately leads to dielectric failure of the insulator through thermal breakdown. Developing self-healing insulation could be a viable option to mitigate permanent mechanical degradation, thus increasing the longevity of the insulation. Instead of relying on catalyst and monomer-filled microcapsules to crack, flow, and cure at the damaged sites described in well-published mechanisms, establishment of ionic crosslinks could allow for multiple healing events to occur with the added benefit of achieving full recovery strength under certain thermal environments. This could be possible if the operating temperature of the insulator is the same as or close to the temperature where ionic crosslinks are formed. Surlyn, a commercial material with ionic crosslinks, was investigated as a candidate self-healing insulator based off prior demonstrations of self-healing behavior. Thin films of varying thicknesses were investigated and the effects of thickness on the dielectric strength were evaluated and compared to representative polymer insulators. The effects of thermal conditioning on the recovery strength and healing were observed as a function of time following dielectric breakdown. Moisture absorption was also studied to determine if moisture absorption rates in Surlyn were lower than that of common polyimides.
NASA Technical Reports Server (NTRS)
Larson, Robert S. (Inventor); Fuller, Michael E. (Inventor)
2013-01-01
Methods of forming an insulating material comprising combining a polysilazane, a cross-linking compound, and a gas-generating compound to form a reaction mixture, and curing the reaction mixture to form a modified polysilazane. The gas-generating compound may be water, an alcohol, an amine, or combinations thereof. The cross-linking compound may be an isocyanate, an epoxy resin, or combinations thereof. The insulating material may include a matrix comprising one of a reaction product of a polysilazane and an isocyanate and a reaction product of a polysilazane and an epoxy resin. The matrix also comprises a plurality of interconnected pores produced from one of reaction of the polysilazane and the isocyanate and from reaction of the polysilazane and the epoxy resin. A precursor formulation that comprises a polysilazane, a cross-linking compound, and a gas-generating compound is also disclosed.
Billi, Fabrizio; Benya, Paul; Kavanaugh, Aaron; Adams, John; Ebramzadeh, Edward; McKellop, Harry
2012-02-01
Numerous studies indicate highly crosslinked polyethylenes reduce the wear debris volume generated by hip arthroplasty acetabular liners. This, in turns, requires new methods to isolate and characterize them. We describe a method for extracting polyethylene wear particles from bovine serum typically used in wear tests and for characterizing their size, distribution, and morphology. Serum proteins were completely digested using an optimized enzymatic digestion method that prevented the loss of the smallest particles and minimized their clumping. Density-gradient ultracentrifugation was designed to remove contaminants and recover the particles without filtration, depositing them directly onto a silicon wafer. This provided uniform distribution of the particles and high contrast against the background, facilitating accurate, automated, morphometric image analysis. The accuracy and precision of the new protocol were assessed by recovering and characterizing particles from wear tests of three types of polyethylene acetabular cups (no crosslinking and 5 Mrads and 7.5 Mrads of gamma irradiation crosslinking). The new method demonstrated important differences in the particle size distributions and morphologic parameters among the three types of polyethylene that could not be detected using prior isolation methods. The new protocol overcomes a number of limitations, such as loss of nanometer-sized particles and artifactual clumping, among others. The analysis of polyethylene wear particles produced in joint simulator wear tests of prosthetic joints is a key tool to identify the wear mechanisms that produce the particles and predict and evaluate their effects on periprosthetic tissues.
Jung, Yun-Chae; Park, Myung-Soo; Kim, Duck-Hyun; Ue, Makoto; Eftekhari, Ali; Kim, Dong-Won
2017-12-13
Amorphous poly(ethylene ether carbonate) (PEEC), which is a copolymer of ethylene oxide and ethylene carbonate, was synthesized by ring-opening polymerization of ethylene carbonate. This route overcame the common issue of low conductivity of poly(ethylene oxide)(PEO)-based solid polymer electrolytes at low temperatures, and thus the solid polymer electrolyte could be successfully employed at the room temperature. Introducing the ethylene carbonate units into PEEC improved the ionic conductivity, electrochemical stability and lithium transference number compared with PEO. A cross-linked solid polymer electrolyte was synthesized by photo cross-linking reaction using PEEC and tetraethyleneglycol diacrylate as a cross-linking agent, in the form of a flexible thin film. The solid-state Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 cell assembled with solid polymer electrolyte based on cross-linked PEEC delivered a high initial discharge capacity of 141.4 mAh g -1 and exhibited good capacity retention at room temperature. These results demonstrate the feasibility of using this solid polymer electrolyte in all-solid-state lithium batteries that can operate at ambient temperatures.
Polyethylene composites containing a phase change material having a C14 straight chain hydrocarbon
Salyer, Ival O.
1987-01-01
A composite useful in thermal energy storage, said composite being formed of a polyethylene matrix having a straight chain alkyl hydrocarbon incorporated therein, said polyethylene being crosslinked to such a degree that said polyethylene matrix is form stable and said polyethylene matrix is capable of absorbing at least 10% by weight of said straight chain alkyl hydrocarbon; the composite is useful in forming pellets or sheets having thermal energy storage characteristics.
Affatato, Saverio; De Mattia, Jonathan Salvatore; Bracco, Pierangiola; Pavoni, Eleonora; Taddei, Paola
2016-12-01
The objective of this study is to evaluate the effects of third-body particles on the in vitro wear behaviour of three different sets of polyethylene acetabular cups after prolonged testing in a hip simulator and accelerated ageing. Vitamin E-blended, cross-linked polyethylene (XLPE_VE), cross-linked polyethylene (XLPE) and conventional polyethylene (STD_PE) acetabular cups were simulator tested for two million cycles under severe conditions (i.e. by adding third-body particles to the bovine calf serum lubricant). Micro-Fourier Transform Infrared and micro-Raman spectroscopic analyses, differential scanning calorimetry, and crosslink density measurements were used to characterize the samples at a molecular level. The STD_PE cups had twice mass loss than the XLPE_VE components and four times than the XLPE samples; statistically significant differences were found between the mass losses of the three sets of cups. The observed wear trend was justified on the basis of the differences in cross-link density among the samples (XLPE>XLPE_VE>STD_PE). FTIR crystallinity profiles, bulk DSC crystallinity and surface micro-Raman crystallinity seemed to have a similar behaviour upon testing: all of them (as well as the all-trans and ortho-trans contents) revealed the most significant changes in XLPE and XLPE_VE samples. The more severe third-body wear testing conditions determined more noticeable changes in all spectroscopic markers with respect to previous tests. Unexpectedly, traces of bulk oxidation were found in both STD_PE (unirradiated) and XLPE (remelting-stabilized), which were expected to be stable to oxidation; on the contrary, XLPE_VE demonstrated a high oxidative stability in the present, highly demanding conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.
Zhao, Jun; Chen, Min; Wang, Xiaoyan; Zhao, Xiaodong; Wang, Zhenwen; Dang, Zhi-Min; Ma, Lan; Hu, Guo-Hua; Chen, Fenghua
2013-06-26
In this paper, the triple shape memory effects (SMEs) observed in chemically cross-linked polyethylene (PE)/polypropylene (PP) blends with cocontinuous architecture are systematically investigated. The cocontinuous window of typical immiscible PE/PP blends is the volume fraction of PE (v(PE)) of ca. 30-70 vol %. This architecture can be stabilized by chemical cross-linking. Different initiators, 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane (DHBP), dicumylperoxide (DCP) coupled with divinylbenzene (DVB) (DCP-DVB), and their mixture (DHBP/DCP-DVB), are used for the cross-linking. According to the differential scanning calorimetry (DSC) measurements and gel fraction calculations, DHBP produces the best cross-linking and DCP-DVB the worst, and the mixture, DHBP/DCP-DVB, is in between. The chemical cross-linking causes lower melting temperature (Tm) and smaller melting enthalpy (ΔHm). The prepared triple shape memory polymers (SMPs) by cocontinuous immiscible PE/PP blends with v(PE) of 50 vol % show pronounced triple SMEs in the dynamic mechanical thermal analysis (DMTA) and visual observation. This new strategy of chemically cross-linked immiscible blends with cocontinuous architecture can be used to design and prepare new SMPs with triple SMEs.
NASA Astrophysics Data System (ADS)
Stroosnijder, Marinus F.; Hoffmann, Michael; Sauvage, Thierry; Blondiaux, Gilbert; Vincent, Laetitia
2005-01-01
Most of today's artificial joints rely on an articulating couple consisting of a CoCrMo alloy and a medical grade polyethylene. The wear of the polyethylene component is the major cause for long-term failure of these prostheses since the wear debris leads to adverse biological reactions. The polyethylene wear is usually measured by gravimetric methods, which are limited due to a low sensitivity and accuracy. To demonstrate the reliability of ultra thin layer activation (UTLA) as an alternative technique, wear tests on a cross-linked ultra-high-molecular weight polyethylene (XLPE) sliding against CoCrMo were performed on a wear tester featuring multi-directional sliding motion. The amount of polyethylene wear was evaluated by both UTLA and gravimetry. The particular TLA method used in this work employed the implantation of 7Be radioactive recoils into the polyethylene surface by means of a light mass particle beam. The results indicate that apart from its relatively high sensitivity, UTLA also offers the possibility for on-line measurements of polyethylene wear. This makes it a viable and complementary technique in wear test studies for medical implant purposes especially for those involving wear resistant materials and for rapid wear screening.
Effect of radiation, heat, and aging on in vitro wear resistance of polyethylene.
Muratoglu, Orhun K; Merrill, Edward W; Bragdon, Charles R; O'Connor, Daniel; Hoeffel, Daniel; Burroughs, Brian; Jasty, Murali; Harris, William H
2003-12-01
Radiation cross-linking increases the wear resistance of polyethylene used in total hip replacement. Radiation also generates residual free radicals, which are detrimental to long-term properties of polyethylene. Two approaches are used to stabilize the residual free radicals and terminally sterilize the components. One is postirradiation annealing with gas sterilization and the other is postirradiation melting with gamma sterilization in nitrogen. The hypothesis of the current study is that postirradiation annealing followed by gamma sterilization in nitrogen will result in more free radicals in polyethylene than gamma sterilization either in air or in nitrogen alone. To test this hypothesis, concentration of residual free radicals was quantified in polyethylene that was annealed and gamma sterilized in nitrogen and control polyethylenes gamma sterilized in air versus in nitrogen. Three crosslinked polyethylenes that were melted and gas sterilized also were included in the study. The effects of residual free radicals were studied by accelerated aging. Oxidation levels and weight loss in bidirectional pin-on-disk tests were determined before and after aging. Polyethylene that was subjected to postirradiation annealing and gamma sterilization resulted in 58% more residual free radicals than control polyethylenes. Weight loss of the annealed polyethylene increased by 16-fold on accelerated aging and had three times higher oxidation levels than that measured in control polyethylenes after aging. In contrast, polyethylenes that were stabilized with postirradiation melting and terminally gas sterilized showed no detectable residual free radicals. Accelerated aging did not affect the weight loss and oxidation levels of melted polyethylenes.
Profile extrusion and mechanical properties of crosslinked wood–thermoplastic composites
Magnus Bengtsson; Kristiina Oksman; Stark Nicole M.
2006-01-01
Challenges for wood-thermoplastic composites to be utilized in structural applications are to lower product weight and to improve the long-term load performance. Silane crosslinking of the composites is one way to reduce the creep during long-term loading and to improve the mechanical properties. In this study, silane crosslinked wood-polyethylene composites were...
NASA Astrophysics Data System (ADS)
Seguchi, Tadao; Tamura, Kiyotoshi; Ohshima, Takeshi; Shimada, Akihiko; Kudoh, Hisaaki
2011-02-01
Radiation and thermal degradation of ethylene-propylene rubber (EPR) and crosslinked polyethylene (XLPE) as cable insulation materials were investigated by evaluating tensile properties, gel-fraction, and swelling ratio, as well as by the infrared (FTIR) analysis. The activation energy of thermal oxidative degradation changed over the range 100-120 °C for both EPR and XLPE. This may be attributed to the fact that the content of an antioxidant used as the stabilizer for polymers decreases by evaporation during thermal ageing at high temperatures. The analysis of antioxidant content and oxidative products in XLPE as a model sample showed that a small amount of antioxidant significantly reduced the extent of thermal oxidation, but was not effective for radiation induced oxidation. The changes in mechanical properties were well reflected by the degree of oxidation. A new model of polymer degradation mechanisms was proposed where the degradation does not take place by chain reaction via peroxy radical and hydro-peroxide. The role of the antioxidant in the polymer is the reduction of free radical formation in the initiation step in thermal oxidation, and it could not stop radical reactions for either radiation or thermal oxidation.
Electron penetration of spacecraft thermal insulation
NASA Technical Reports Server (NTRS)
Powers, W. L.; Adams, B. F.; Inouye, G. T.
1981-01-01
The external thermal blanket with 13 mils of polyethylene which has the known range and stopping power as a function of electron energy is investiated. The most recent omnidirectional peak Jovian electron flux at 5 Jupiter radii is applied, the electron current penetrating the thermal blanket is calculated and allowed to impinge on a typical 20 mil polyethylene insulator surrounding a wire. The radiation dose rate to the insulator is then calculated and the electrical conductivity found. The results demonstrate that the increased electronic mobility is sufficient to keep the maximum induced electric field two orders of magnitude below the critical breakdown strength.
Improved Aerogel Vacuum Thermal Insulation
NASA Technical Reports Server (NTRS)
Ruemmele, Warren P.; Bue, Grant C.
2009-01-01
An improved design concept for aerogel vacuum thermal-insulation panels calls for multiple layers of aerogel sandwiched between layers of aluminized Mylar (or equivalent) poly(ethylene terephthalate), as depicted in the figure. This concept is applicable to both the rigid (brick) form and the flexible (blanket) form of aerogel vacuum thermal-insulation panels. Heretofore, the fabrication of a typical aerogel vacuum insulating panel has involved encapsulation of a single layer of aerogel in poly(ethylene terephthalate) and pumping of gases out of the aerogel-filled volume. A multilayer panel according to the improved design concept is fabricated in basically the same way: Multiple alternating layers of aerogel and aluminized poly(ethylene terephthalate) are assembled, then encapsulated in an outer layer of poly(ethylene terephthalate), and then the volume containing the multilayer structure is evacuated as in the single-layer case. The multilayer concept makes it possible to reduce effective thermal conductivity of a panel below that of a comparable single-layer panel, without adding weight or incurring other performance penalties. Implementation of the multilayer concept is simple and relatively inexpensive, involving only a few additional fabrication steps to assemble the multiple layers prior to evacuation. For a panel of the blanket type, the multilayer concept, affords the additional advantage of reduced stiffness.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Duckworth, Robert C.; Frame, Emily; Fifield, Leonard S.
As part of the Light Water Reactor and Sustainability (LWRS) program in the U.S. Department of Energy (DOE) Office of Nuclear Energy, material aging and degradation research is currently geared to support the long-term operation of existing nuclear power plants (NPPs) as they move beyond their initial 40 year licenses. The goal of this research is to provide information so that NPPs can develop aging management programs (AMPs) to address replacement and monitoring needs as they look to operate for 20 years, and in some cases 40 years, beyond their initial operating lifetimes. For cable insulation and jacket materials thatmore » support instrument, control, and safety systems, accelerated aging data are needed to determine priorities in cable aging management programs. Before accelerated thermal and radiation aging of harvested, representative cable insulation and jacket materials, the benchmark performance of a new test capability at Oak Ridge National Laboratory (ORNL) was evaluated for temperatures between 70 and 135°C, dose rates between 100 and 500 Gy/h, and accumulated doses up to 20 kGy, Samples that were characterized and are representative of current materials in use were harvested from the Callaway NPP near Fulton, Missouri, and the San Onofre NPP north of San Diego, California. From the Callaway NPP, a multiconductor control rod cable manufactured by Boston Insulated Wire (BIW), with a Hypalon/ chorolosulfonated polyethylene (CSPE) jacket and ethylene-propylene rubber (EPR) insulation, was harvested from the auxiliary space during a planned outage in 2013. This cable was placed into service when the plant was started in 1984. From the San Onofre NPP, a Rockbestos Firewall III (FRIII) cable with a Hypalon/ CSPE jacket with cross-linked polyethylene (XLPE) insulation was harvested from an on-site, climate-controlled storage area. This conductor, which was never placed into service, was procured around 2007 in anticipation of future operation that did not occur. Benchmark aging for both jacket and insulation material was carried out in air at a temperature of 125°C or in uniform 140 Gy/h gamma irradiation over a period of 60 days. Their mechanical properties over the course of their exposures were compared with reference data from comparable cable jacket/insulation compositions and aging conditions. For both accelerated thermal and radiation aging, it was observed that the mechanical properties for the Callaway BIW control rod cable were consistent with those previously measured. However, for the San Onofre Rockbestos FRIII, there was an observable functional difference for accelerated thermal aging at 125°C. Details on possible sources for this difference and plans for resolving each source are given in this paper.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Duckworth, Robert C; Fifield, Dr Leonard S
As part of the Light Water Reactor and Sustainability (LWRS) program in the U.S. Department of Energy (DOE) Office of Nuclear Energy, material aging and degradation research is currently geared to support the long-term operation of existing nuclear power plants (NPPs) as they move beyond their initial 40 year licenses. The goal of this research is to provide information so that NPPs can develop aging management programs (AMPs) to address replacement and monitoring needs as they look to operate for 20 years, and in some cases 40 years, beyond their initial operating lifetimes. For cable insulation and jacket materials thatmore » support instrument, control, and safety systems, accelerated aging data are needed to determine priorities in cable aging management programs. Before accelerated thermal and radiation aging of harvested, representative cable insulation and jacket materials, the benchmark performance of a new test capability at Oak Ridge National Laboratory (ORNL) was evaluated for temperatures between 70 and 135 C, dose rates between 100 and 500 Gy/h, and accumulated doses up to 20 kGy, Samples that were characterized and are representative of current materials in use were harvested from the Callaway NPP near Fulton, Missouri, and the San Onofre NPP north of San Diego, California. From the Callaway NPP, a multiconductor control rod cable manufactured by Boston Insulated Wire (BIW), with a Hypalon/ chorolosulfonated polyethylene (CSPE) jacket and ethylene-propylene rubber (EPR) insulation, was harvested from the auxiliary space during a planned outage in 2013. This cable was placed into service when the plant was started in 1984. From the San Onofre NPP, a Rockbestos Firewall III (FRIII) cable with a Hypalon/ CSPE jacket with cross-linked polyethylene (XLPE) insulation was harvested from an on-site, climate-controlled storage area. This conductor, which was never placed into service, was procured around 2007 in anticipation of future operation that did not occur. Benchmark aging for both jacket and insulation material was carried out in air at a temperature of 125 C or in uniform 140 Gy/h gamma irradiation over a period of 60 days. Their mechanical properties over the course of their exposures were compared with reference data from comparable cable jacket/insulation compositions and aging conditions. For both accelerated thermal and radiation aging, it was observed that the mechanical properties for the Callaway BIW control rod cable were consistent with those previously measured. However, for the San Onofre Rockbestos FRIII, there was an observable functional difference for accelerated thermal aging at 125 C. Details on possible sources for this difference and plans for resolving each source are given in this paper.« less
On the mechanism of charge transport in low density polyethylene
NASA Astrophysics Data System (ADS)
Upadhyay, Avnish K.; Reddy, C. C.
2017-08-01
Polyethylene based polymeric insulators, are being increasingly used in the power industry for their inherent advantages over conventional insulation materials. Specifically, modern power cables are almost made with these materials, replacing the mass-impregnated oil-paper cable technology. However, for ultra-high dc voltage applications, the use of these polymeric cables is hindered by ununderstood charge transport and accumulation. The conventional conduction mechanisms (Pool-Frenkel, Schottky, etc.) fail to track high-field charge transport in low density polyethylene, which is semi-crystalline in nature. Until now, attention was devoted mainly to the amorphous region of the material. In this paper, authors propose a novel mechanism for conduction in low density polyethylene, which could successfully track experimental results. As an implication, a novel, substantial relationship is established for electrical conductivity that could be effectively used for understanding conduction and breakdown in polyethylene, which is vital for successful development of ultra-high voltage dc cables.
NASA Astrophysics Data System (ADS)
Wilson, John Ford
1997-09-01
Ultra high molecular weight polyethylene (UHMW-PE) is used extensively in hip and knee endoprostheses. Radiation damage from the sterilization of these endoprostheses prior to surgical insertion results in polymer crosslinking and decreased oxidative stability. The motivation for this study was to determine if UHMW-PE could be crosslinked by low dose proton irradiation with minimal radiation damage and its subsequent deleterious effects. I found that low dose proton irradiation and post irradiation hydrogen annealing did crosslink UHMW-PE and limit post irradiation oxidation. Crosslinking onset was investigated for UHMW-PE irradiated with 2.6 and 30 MeV H+ ions at low doses from 5.7 × 1011-2.3 × 1014 ions/cm2. Crosslinking was determined from gel permeation chromatography (GPC) of 1,2,4 trichlorobenzene sol fractions and increased with dose. Fourier transform infrared spectroscopy (FTIR) showed irradiation resulted in increased free radicals confirmed from increased carbonyl groups. Radiation damage, especially at the highest doses observed, also showed up in carbon double bonds and increased methyl end groups. Hydrogen annealing after ion irradiation resulted in 40- 50% decrease in FTIR absorption associated with carbonyl. The hydrogen annealing prevented further oxidation after aging for 1024 hours at 80oC. Hydrogen annealing was successful in healing radiation damage through reacting with the free radicals generated during proton irradiation. Polyethylenes, polyesters, and polyamides are used in diverse applications by the medical profession in the treatment of orthopedic impairments and cardiovascular disease and for neural implants. These artificial implants are sterilized with gamma irradiation prior to surgery and the resulting radiation damage can lead to accelerated deterioration of the implant properties. The findings in this study will greatly impact the continued use of these materials through the elimination of many problems associated with radiation damage from sterilization. The higher energy transfer for proton compared to gamma irradiation greatly accelerated the radiation damage. Radiation damage increased linearly with dose over the range of doses examined. These results were consistent with findings from earlier researchers of gamma irradiation of polyethylene.
NASA Technical Reports Server (NTRS)
Tigelaar, Dean M.; Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.
2005-01-01
A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.
Hip Resurfacing Using Highly Cross-linked Polyethylene: Prospective Study Results at 8.5 Years.
Pritchett, James W
2016-10-01
Hip resurfacing is an option to consider when treating younger, more active patients. Advantages over total hip arthroplasty include a more normal gait and a lower incidence of thigh pain. In this prospective study, 190 hip resurfacing procedures (164 participants) were performed using a cobalt-chromium femoral component and a cementless acetabular cup with a 3.8-mm highly cross-linked polyethylene acetabular liner. The mean follow-up was 8.5 (range, 7-10) years. Two participants were lost to follow-up and 2 died. One participant underwent successful revision surgery for acetabular loosening. Four participants underwent successful revision to a total hip arthroplasty because of femoral neck fracture (2), femoral loosening, or infection. The Kaplan-Meier survivorship was 97%. Acetabular bone conservation was assessed using computed tomography by measuring the medial acetabular wall. The mean thickness was 9 mm. Femoral bone was well preserved with a mean head:neck ratio of 1.37. There were 4 (2%) osteolytic defects up to 0.9 cm(3) on computed tomography and no instances of impending polyethylene wear-through. Seven polyethylene retrievals had a measured wear rate of 0.05 mm/y. Hip resurfacing using a highly cross-linked polyethylene acetabular component is a reliable procedure. Both femoral and acetabular bones are reasonably preserved compared with prior resurfacing methods. The low incidence of osteolysis and the low rate of wear found on retrievals suggest that many years of use in highly active patients is possible. Copyright © 2016 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Cantor, Kirk Martin
1998-12-01
Moisture-crosslinkable polyethylene used in the extrusion coating of electrical cable has many advantages over other polymer systems used for crosslinked cable coating. However, one of its major drawbacks is the long cure times required. The purpose of this study was to describe how curing takes place in cable systems using moisture-crosslinkable polyethylene, with an ultimate goal of gaining insight into how cure times might be reduced. Crosslinking was investigated with an emphasis on how the curing reaction proceeds through the coating, using analyses to characterize processing conditions and resulting mechanical and structural properties. In the design of the study, material compounds were varied as were curing conditions. Cable coatings were sectioned by position through the coating thickness and characterized using several techniques. Mechanical, thermal, and structural properties of the polymer coating were measured. A significant finding from the study was that the degree of cure was highest at positions in the coating closest to the conductor. Because this was opposite to what was expected, an investigation into the cause of this finding was pursued. It was found that during cure at elevated temperature, the inside surface of the coating remains at a generally higher temperature than the outside surface. This provides a more favorable cure condition for positions in the coating closest to the conductor. Based on the results of this study, a list of suggested follow-up studies is provided at the end of the dissertation. One proposal for investigating reduced cure times involves providing heat to the interior of the cable during cure.
Brockett, Claire L; Abdelgaied, Abdellatif; Haythornthwaite, Tony; Hardaker, Catherine; Fisher, John; Jennings, Louise M
2016-01-01
Advancements in knee replacement design, material and sterilisation processes have provided improved clinical results. However, surface wear of the polyethylene leading to osteolysis is still considered the longer-term risk factor. Experimental wear simulation is an established method for evaluating the wear performance of total joint replacements. The aim of this study was to investigate the influence of simulation input conditions, specifically input kinematic magnitudes, waveforms and directions of motion and position of the femoral centre of rotation, on the wear performance of a fixed-bearing total knee replacement through a combined experimental and computational approach. Studies were completed using conventional and moderately cross-linked polyethylene to determine whether the influence of these simulation input conditions varied with material. The position of the femoral centre of rotation and the input kinematics were shown to have a significant influence on the wear rates. Similar trends were shown for both the conventional and moderately cross-linked polyethylene materials, although lower wear rates were found for the moderately cross-linked polyethylene due to the higher level of cross-linking. The most important factor influencing the wear was the position of the relative contact point at the femoral component and tibial insert interface. This was dependent on the combination of input displacement magnitudes, waveforms, direction of motion and femoral centre of rotation. This study provides further evidence that in order to study variables such as design and material in total knee replacement, it is important to carefully control knee simulation conditions. This can be more effectively achieved through the use of displacement control simulation. PMID:27160561
Carbon Nanofiber Incorporated Silica Based Aerogels with Di-Isocyanate Cross-Linking
NASA Technical Reports Server (NTRS)
Vivod, Stephanie L.; Meador, Mary Ann B.; Capadona, Lynn A.; Sullivan, Roy M.; Ghosn, Louis J.; Clark, Nicholas; McCorkle, Linda
2008-01-01
Lightweight materials with excellent thermal insulating properties are highly sought after for a variety of aerospace and aeronautic applications. (1) Silica based aerogels with their high surface area and low relative densities are ideal for applications in extreme environments such as insulators for the Mars Rover battery. (2) However, the fragile nature of aerogel monoliths prevents their widespread use in more down to earth applications. We have shown that the fragile aerogel network can be cross-linked with a di-isocyanate via amine decorated surfaces to form a conformal coating. (3) This coating reinforces the neck regions between secondary silica particles and significantly strengthens the aerogels with only a small effect on density or porosity. Scheme 1 depicts the cross-linking reaction with the di-isocyanate and exhibits the stages that result in polymer cross-linked aerogel monoliths.
Thermal overload characteristics of extruded dielectric cables: Final report
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dima, A.; Katz, C.; Eager, G.S. Jr.
1988-06-01
This report addresses characteristics of thermoset extruded dielectric power cables in the 15--35 kV class, operated under thermal overload conditions. It presents a methodical study to determine the suitability of extruded type cable for operation at elevated temperatures. The results provide utilities with knowledge on the behavior of thermoset insulated cables at temperatures in the 130 to 175/degree/C conductor temperature range. Present industry specifications recommend a maximum emergency conductor temperature of 130/degree/C. The suitability of this temperature and the time it is to be maintained had been questioned. The present report indicates that crosslinked polyethylene and ethylene propylene insulated cable,more » both new and service aged, are suitable for emergency operation during extended periods at 130/degree/C. When these cables are provided with polyvinyl chloride jackets, long term exposure to temperatures greater than 130/degree/C can adversely affect the integrity of the jacket. Investigations on new cables were performed on short samples in ovens and on long samples in simulated ducts in the laboratory and in a typical utility duct bank. Investigations on cables recovered from service were performed in the laboratory with the cables installed in simulated ducts. 10 refs., 49 figs., 73 tabs.« less
Wear of a 5 megarad cross-linked polyethylene liner: a 6-year RSA study.
Callary, Stuart A; Campbell, David G; Mercer, Graham; Nilsson, Kjell G; Field, John R
2013-07-01
One cross-linked polyethylene (XLPE) liner is manufactured using a lower dose of radiation, 5 Mrad, which may result in less cross-linking. The reported in vivo wear rate of this XLPE liner in patients undergoing THA has varied, and has included some patients in each reported cohort who had greater than 0.1 mm/year of wear, which is an historical threshold for osteolysis. Previous studies have measured wear on plain radiographs, an approach that has limited sensitivity. We therefore measured the amount and direction of wear at 6 years using Radiostereometric analysis (RSA) in patients who had THAs that included a cross-linked polyethylene liner manufactured using 5 Mrad radiation. We prospectively reviewed wear in 30 patients who underwent primary THAs with the same design of cross-linked acetabular liner and a 28-mm articulation. Tantalum markers were inserted during surgery and all patients had RSA radiographic examinations at 1 week, 6 months, 1, 2, and 6 years postoperatively. The mean proximal, two-dimensional (2-D) and three-dimensional (3-D) wear rates calculated between 1 year and 6 years were 0.014, 0.014, and 0.018 mm/per year, respectively. The direction of the head penetration recorded between 1 week and 6 years was in a proximal direction for all patients, proximolateral for 16 of 24 patients, and proximomedial for eight of 24 patients. The proximal, 2-D and 3-D wear of a XLPE liner produced using 5 Mrad of radiation was low but measurable by RSA after 6 years. No patients had proximal 2-D or 3-D wear rates exceeding 0.1 mm/year. Further followup is needed to evaluate the effect of XLPE wear particles on the development of long-term osteolysis.
Gencur, Sara J; Rimnac, Clare M; Kurtz, Steven M
2006-03-01
To prolong the life of total joint replacements, highly crosslinked ultra-high molecular weight polyethylenes (UHMWPEs) have been introduced to improve the wear resistance of the articulating surfaces. However, there are concerns regarding the loss of ductility and potential loss in fatigue crack propagation (FCP) resistance. The objective of this study was to evaluate the effects of gamma radiation-induced crosslinking with two different post-irradiation thermal treatments on the FCP resistance of UHMWPE. Two highly crosslinked and one virgin UHMWPE treatment groups (ram-extruded, orthopedic grade, GUR 1050) were examined. For the two highly crosslinked treatment groups, UHMWPE rods were exposed to 100 kGy and then underwent post-irradiation thermal processing either above the melt temperature or below the melt temperature (2 h-150 degrees C, 110 degrees C). Compact tension specimens were cyclically loaded to failure and the fatigue crack growth rate, da/dN, vs. cyclic stress intensity factor, DeltaK, behavior was determined and compared between groups. Scanning electron microscopy was used to examine fracture surface characteristics. Crosslinking was found to decrease the ability of UHMWPE to resist crack inception and propagation under cyclic loading. The findings also suggested that annealing as a post-irradiation treatment may be somewhat less detrimental to FCP resistance of UHMWPE than remelting. Scanning electron microscopy examination of the fracture surfaces demonstrated that the virgin treatment group failed in a more ductile manner than the two highly crosslinked treatment groups.
Application of Optical Diagnosis to Aged Low-Voltage Cable Insulation in Nuclear Plants
NASA Astrophysics Data System (ADS)
Katagiri, Junichi; Takezawa, Yoshitaka; Shouji, Hiroshi
We have developed a novel non-destructive optical diagnosis technique for low-voltage cable insulations used in nuclear power plants. The key features of this diagnosis are the use of two wavelengths to measure the change in reflective absorbance (ΔAR), the use of polarized light to measure crystallinity and the use of element volatilizing to measure fluorescence. Chemical kinetics is used to predict the lifetimes of the cable insulations. When cable insulations darken and harden by time degradation, the ΔAR and depolarization parameters increase. This means that the cross-linking density in the cable insulations increases due to deterioration reactions. When the cross-linking density of insulation increases, its elasticity, corresponding to the material's life, increases. Similarly, as the crystallinity increases due to the change in the high-order structure of the insulating resin caused by irradiation, its elongation property decreases. The elongation property of insulation is one of the most important parameters that can be used to evaluate material lifetimes, because it relates to elasticity. The ΔAR correlated with the elongation property, and the correlation coefficient of an accelerated experiment using model pieces was over 0.9. Thus, we concluded that this optical diagnosis should be applied to evaluate the degradation of cable insulations used in nuclear power plants.
7 CFR 1728.204 - Electric standards and specifications for materials and construction.
Code of Federal Regulations, 2014 CFR
2014-01-01
... application where additional insulation is desired. (1) The cable may be used in single-phase, two (V)-phase... polyethylene (TR-XLPE) insulation compound containing an additive, a polymer modification filler, which helps... shield shall have a nominal operating temperature equal to, or higher than, that of the insulation. (e...
7 CFR 1728.204 - Electric standards and specifications for materials and construction.
Code of Federal Regulations, 2013 CFR
2013-01-01
... application where additional insulation is desired. (1) The cable may be used in single-phase, two (V)-phase... polyethylene (TR-XLPE) insulation compound containing an additive, a polymer modification filler, which helps... shield shall have a nominal operating temperature equal to, or higher than, that of the insulation. (e...
Crosslinked crystalline polymer and methods for cooling and heating
Salyer, Ival O.; Botham, Ruth A.; Ball, III, George L.
1980-01-01
The invention relates to crystalline polyethylene pieces having optimum crosslinking for use in storage and recovery of heat, and it further relates to methods for storage and recovery of heat using crystalline polymer pieces having optimum crosslinking for these uses. Crystalline polymer pieces are described which retain at least 70% of the heat of fusion of the uncrosslinked crystalline polymer and yet are sufficiently crosslinked for the pieces not to stick together upon being cycled above and below the melting point of said polymer, preferably at least 80% of the heat of fusion with no substantial sticking together.
Jing, Ziang; Li, Changming; Zhao, Hong; Zhang, Guiling; Han, Baozhong
2016-01-01
The doping effect of graphene nanoplatelets (GNPs) on electrical insulation properties of polyethylene (PE) was studied by combining experimental and theoretical methods. The electric conduction properties and trap characteristics were tested for pure PE and PE/GNPs composites by using a direct measurement method and a thermal stimulated current (TSC) method. It was found that doping smaller GNPs is more beneficial to decrease the conductivity of PE/GNPs. The PE/GNPs composite with smaller size GNPs mainly introduces deep energy traps, while with increasing GNPs size, besides deep energy traps, shallow energy traps are also introduced. These results were also confirmed by density functional theory (DFT) and the non-equilibrium Green’s function (NEGF) method calculations. Therefore, doping small size GNPs is favorable for trapping charge carriers and enhancing insulation ability, which is suggested as an effective strategy in exploring powerful insulation materials. PMID:28773802
Pourrahimi, Amir Masoud; Olsson, Richard T; Hedenqvist, Mikael S
2018-01-01
Recent progress in the development of polyethylene/metal-oxide nanocomposites for extruded high-voltage direct-current (HVDC) cables with ultrahigh electric insulation properties is presented. This is a promising technology with the potential of raising the upper voltage limit in today's underground/submarine cables, based on pristine polyethylene, to levels where the loss of energy during electric power transmission becomes low enough to ensure intercontinental electric power transmission. The development of HVDC insulating materials together with the impact of the interface between the particles and the polymer on the nanocomposites electric properties are shown. Important parameters from the atomic to the microlevel, such as interfacial chemistry, interfacial area, and degree of particle dispersion/aggregation, are discussed. This work is placed in perspective with important work by others, and suggested mechanisms for improved insulation using nanoparticles, such as increased charge trap density, adsorption of impurities/ions, and induced particle dipole moments are considered. The effects of the nanoparticles and of their interfacial structures on the mechanical properties and the implications of cavitation on the electric properties are also discussed. Although the main interest in improving the properties of insulating polymers has been on the use of nanoparticles, leading to nanodielectrics, it is pointed out here that larger microscopic hierarchical metal-oxide particles with high surface porosity also impart good insulation properties. The impact of the type of particle and its inherent properties (purity and conductivity) on the nanocomposite dielectric and insulating properties are also discussed based on data obtained by a newly developed technique to directly observe the charge distribution on a nanometer scale in the nanocomposite. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Crosslinked, porous, polyacrylate beads
NASA Technical Reports Server (NTRS)
Rembaum, Alan (Inventor); Yen, Shiao-Ping Siao (Inventor); Dreyer, William J. (Inventor)
1976-01-01
Uniformly-shaped, porous, round beads are prepared by the co-polymerization of an acrylic monomer and a cross-linking agent in the presence of 0.05 to 5% by weight of an aqueous soluble polymer such as polyethylene oxide. Cross-linking proceeds at high temperature above about 50.degree.C or at a lower temperature with irradiation. Beads of even shape and even size distribution of less than 2 micron diameter are formed. The beads will find use as adsorbents in chromatography and as markers for studies of cell surface receptors.
Crosslinked, porous, polyacrylate beads
NASA Technical Reports Server (NTRS)
Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Dreyer, William J. (Inventor)
1977-01-01
Uniformly-shaped, porous, round beads are prepared by the co-polymerization of an acrylic monomer and a cross-linking agent in the presence of 0.05 to 5% by weight of an aqueous soluble polymer such as polyethylene oxide. Cross-linking proceeds at high temperature above about 50.degree. C or at a lower temperature with irradiation. Beads of even shape and even size distribution of less than 2 micron diameter are formed. The beads will find use as adsorbents in chromatography and as markers for studies of cell surface receptors.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Duckworth, Robert C; Aytug, Tolga; Paranthaman, Mariappan Parans
2015-01-01
Cross-linked polyethylene (XLPE) nanocomposites have been developed in an effort to improve cable insulation lifetime to serve in both instrument cables and auxiliary power systems in advanced reactor applications as well as to provide an alternative for new or retro-fit cable insulation installations. Nano-dielectrics composed of different weight percentages of MgO & SiO 2 have been subjected to radiation at accumulated doses approaching 20 MRad and thermal aging temperatures exceeding 100 C. Depending on the composition, the performance of the nanodielectric insulation was influenced, both positively and negatively, when quantified with respect to its electrical and mechanical properties. For virginmore » unradiated or thermally aged samples, XLPE nanocomposites with 1wt.% SiO 2 showed improvement in breakdown strength and reduction in its dissipation factor when compared to pure undoped XLPE, while XLPE 3wt.% SiO 2 resulted in lower breakdown strength. When aged in air at 120 C, retention of electrical breakdown strength and dissipation factor was observed for XLPE 3wt.% MgO nanocomposites. Irrespective of the nanoparticle species, XLPE nanocomposites that were gamma irradiated up to the accumulated dose of 18 MRad showed a significant drop in breakdown strength especially for particle concentrations greater than 3 wt.%. Additional attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy measurements suggest changes in the structure of the XLPE SiO 2 nanocomposites associated with the interaction of silicon and oxygen. Discussion on the relevance of property changes with respect to cable aging and condition monitoring is presented.« less
NASA Astrophysics Data System (ADS)
Boukezzi, L.; Rondot, S.; Jbara, O.; Boubakeur, A.
2018-08-01
The effect of thermal aging on the charging phenomena in cross-linked polyethylene (XLPE) has been studied under electron beam irradiation in scanning electron microscope (SEM). The dynamic variation of trapped charge represents the trapping process of XLPE under electron beam irradiation. We have found that the trapped charge variation can be approximated by a first order exponential function. The amount of trapped charge presents enhanced values at the beginning of aging at lower temperatures (80 °C and 100 °C). This suggests the diffusion of cross-linking by-products to the surface of sample that acts as traps for injected electrons. The oxidation which is a very important form of XLPE degradation has an effect at the advanced stage of the aging process. For higher temperatures (120 °C and 140 °C), the taken part process in the evolution of the trapped charge is the crystallinity increase at the beginning of aging leading to the trapped charge decreasing, and the polar groups generated by thermo-oxidation process at the end of aging leading to the trapped charge increase. Variations of leakage current according to the aging time have quite similar trends with the dielectric losses factor and consequently some correlations must be made between charging mechanisms and the electrical behaviour of XLPE under thermal aging.
Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes
Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...
2018-10-02
Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less
Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kusuma, Victor A.; Macala, Megan K.; Liu, Jian
Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less
Epinette, Jean-Alain; Harwin, Steven F; Rowan, Fiachra E; Tracol, Philippe; Mont, Michael A; Chughtai, Morad; Westrich, Geoffrey H
2017-03-01
To evaluate early performance of contemporary dual mobility acetabular systems with second generation annealed highly cross-linked polyethylene for primary hip arthroplasty of patients under 55 years of age. A prospective observational five years study across five centers in Europe and the USA of 321 patients with a mean age of 48.1 years was performed. Patients were assessed for causes of revision, hip instability, intra-prosthetic dissociation, Harris hip score and radiological signs of osteolysis. There were no dislocations and no intra-prosthetic dissociations. Kaplan Meier analysis demonstrated 97.51% survivorship for all cause revision and 99.68% survivorship for acetabular component revision at five years. Mean Harris hip score was 93.6. Two acetabular shells were revised for neck-rim implant impingement without dislocation and ten femoral stems were revised for causes unrelated to dual mobility implants. Contemporary highly cross-linked polyethylene dual mobility systems demonstrate excellent early clinical, radiological, and survivorship results in a cohort of patients that demand high performance from their implants. It is envisaged that DM and second generation annealed HXLPE may reduce THA instability and wear, the two most common causes of THA revision in hip arthroplasty.
Properties of crosslinked ultra-high-molecular-weight polyethylene.
Lewis, G
2001-02-01
Substantially reducing the rate of generation of wear particles at the surfaces of ultra-high-molecular-weight polyethylene (UHMWPE) orthopedic implant bearing components, in vivo, is widely regarded as one of the most formidable challenges in modern arthroplasty. In the light of this, much research attention has been paid to the myriad of endogenous and exogenous factors that have been postulated to affect this wear rate, one such factor being the polymer itself. In recent years, there has been a resurgence of interest in crosslinking the polymer as a way of improving its properties that are considered relevant to its use for fabricating bearing components. Such properties include wear resistance, fatigue life, and fatigue crack propagation rate. Although a large volume of literature exists on the topic on the impact of crosslinking on the properties of UHMWPE, no critical appraisal of this literature has been published. This is one of the goals of the present article, which emphasizes three aspects. The first is the trade-off between improvement in wear resistance and depreciation in other mechanical and physical properties. The second aspect is the presentation of a method of estimating the optimal value of a crosslinking process variable (such as dose in radiation-induced crosslinking) that takes into account this trade-off. The third aspect is the description of a collection of under- and unexplored research areas in the field of crosslinked UHMWPE, such as the role of starting resin on the properties of the crosslinked polymer, and the in vitro evaluation of the wear rate of crosslinked tibial inserts and other bearing components that, in vivo, are subjected to nearly unidirectional motion.
The wear of cross-linked polyethylene against itself.
Joyce, T J; Ash, H E; Unsworth, A
1996-01-01
Cross-linked polyethylene (XLPE) may have an application as a material for an all-plastic surface replacement finger joint. It is inexpensive, biocompatible and can be injection-moulded into the complex shapes that are found on the ends of the finger bones. Further, the cross-linking of polyethylene has significantly improved its mechanical properties. Therefore, the opportunity exists for an all-XLPE joint, and so the wear characteristics of XLPE sliding against itself have been investigated. Wear tests were carried out on both reciprocating pin-on-plate machines and a finger function simulator. The reciprocating pin-on-plate machines had pins loaded at 10 N and 40 N. All pin-on-plate tests show wear factors from the plates very much greater than those of the pins. After 349 km of sliding, a mean wear factor of 0.46 x 10(-6) mm3/N m was found for the plates compared with 0.021 x 10(-6) mm3/N m for the pins. A fatigue mechanism may be causing this phenomenon of greater plate wear. Tests using the finger function simulator give an average wear rate of 0.22 x 10(-6) mm3/N m after 368 km. This sliding distance is equivalent to 12.5 years of use in vivo. The wear factors found were comparable with those of ultra-high molecular weight polyethylene (UHMWPE) against a metallic counterface and, therefore, as the loads across the finger joint are much less than those across the knee or the hip, it is probable that an all-XLPE finger joint will be viable from a wear point of view.
Hydrogels of poly(ethylene glycol): mechanical characterization and release of a model drug.
Iza, M; Stoianovici, G; Viora, L; Grossiord, J L; Couarraze, G
1998-03-02
Thermosensitive polymer networks were synthesized from poly(ethylene glycol), hexamethylene diisocyanate and 1,2,6-hexanetriol in stoichiometric proportions. By varying the amount of 1,2,6-hexanetriol and the molar mass of the poly(ethylene glycol), a wide range of networks with different crosslinking densities was prepared. The networks obtained were characterized by the temperature dependence of their degree of equilibrium swelling in water and by their Young's moduli. For each network, the molecular weight between crosslinks was estimated. The structure of the hydrogels was analysed with respect to scaling laws, and it was found that the results obtained with PEG 1500 and PEG 6000 hydrogels are in agreement with theoretical predictions, whereas those obtained with PEG 400 hydrogels are in disagreement. The release properties of PEG hydrogels were studied by the determination of the diffusion coefficient for acebutolol chlorhydrate and by an analysis of the effect of temperature on these coefficients. Finally, these release properties were correlated with the swelling and structural properties of the hydrogels.
SLIDING DIRECTION-DEPENDENCE OF POLYETHYLENE WEAR FOR METAL COUNTERFACE TRAVERSE OF SEVERE SCRATCHES
Glennon, Liam P.; Baer, Thomas E.; Martin, James A.; Lack, William D.; Brown, Thomas D.
2008-01-01
Third body effects appear to be responsible for an appreciable portion of the wear rate variability within cohorts of patients with metal-on-polyethylene joint replacements. The parameters dominating the rate of polyethylene debris liberation by counterface scratches are not fully understood, but one seemingly contributory factor is the scratch’s orientation relative to the direction of instantaneous local surface sliding. To study this influence, arrays of 550 straight parallel scratches each representative of the severe end of the clinical range were diamond stylus-ruled onto the surface of polished stainless steel plates. These ruled plates were then worn reciprocally against polyethylene pins (both conventional and highly cross-linked) at traverse angles varied parametrically relative to the scratch direction. Wear was measured gravimetrically, and particulate debris was harvested and morphologically characterized. Both of the polyethylene variants tested showed pronounced wear rate peaks at acute scratch traverse angles (15º for conventional, 5º for cross-linked), and had nominally comparable absolute wear rate magnitudes. The particulate debris from this very aggressive test regime primarily consisted of extremely large and elongated strands, often tens or even hundreds of microns in length. These data suggest that counterface damage regions with preferential scratch directionality can liberate large amounts of polyethylene debris, apparently by a slicing/shearing mechanism, at critical (acute) attack angles. However, the predominant manifestation of this wear volume was in the form of particles far beyond the most osteolytically potent size range. PMID:19045513
CuC1 thermochemical cycle for hydrogen production
Fan, Qinbai [Chicago, IL; Liu, Renxuan [Chicago, IL
2012-01-03
An electrochemical cell for producing copper having a dense graphite anode electrode and a dense graphite cathode electrode disposed in a CuCl solution. An anion exchange membrane made of poly(ethylene vinyl alcohol) and polyethylenimine cross-linked with a cross-linking agent selected from the group consisting of acetone, formaldehyde, glyoxal, glutaraldehyde, and mixtures thereof is disposed between the two electrodes.
Zustiak, Silviya P.
2011-01-01
The objective of this work was to create three-dimensional (3D) hydrogel matrices with defined mechanical properties, as well as tunable degradability for use in applications involving protein delivery and cell encapsulation. Thus, we report the synthesis and characterization of a novel hydrolytically degradable poly(ethylene glycol) (PEG) hydrogel composed of PEG vinyl sulfone (PEG-VS) cross-linked with PEG-diester-dithiol. Unlike previously reported degradable PEG-based hydrogels, these materials are homogeneous in structure, fully hydrophilic and have highly specific cross-linking chemistry. We characterized hydrogel degradation and associated trends in mechanical properties, i.e., storage modulus (G′), swelling ratio (QM), and mesh size (ξ). Degradation time and the monitored mechanical properties of the hydrogel correlated with cross-linker molecular weight, cross-linker functionality, and total polymer density; these properties changed predictably as degradation proceeded (G′ decreased, whereas QM and ξ increased) until the gels reached complete degradation. Balb/3T3 fibroblast adhesion and proliferation within the 3D hydrogel matrices were also verified. In sum, these unique properties indicate that the reported degradable PEG hydrogels are well poised for specific applications in protein and cell delivery to repair soft tissue. PMID:20355705
Sircar, S; Aisenbrey, E; Bryant, S J; Bortz, D M
2015-01-07
We present an experimentally guided, multi-phase, multi-species polyelectrolyte gel model to make qualitative predictions on the equilibrium electro-chemical properties of articular cartilage. The mixture theory consists of two different types of polymers: poly(ethylene gylcol) (PEG), chondrotin sulfate (ChS), water (acting as solvent) and several different ions: H(+), Na(+), Cl(-). The polymer chains have covalent cross-links whose effect on the swelling kinetics is modeled via Doi rubber elasticity theory. Numerical studies on equilibrium polymer volume fraction and net osmolarity (difference in the solute concentration across the gel) show a complex interplay between ionic bath concentrations, pH, cross-link fraction and the average charge per monomer. Generally speaking, swelling is aided due to a higher average charge per monomer (or a higher particle fraction of ChS, the charged component of the polymer), low solute concentration in the bath, a high pH or a low cross-link fraction. A peculiar case arises at higher values of cross-link fraction, where it is observed that increasing the average charge per monomer leads to gel deswelling. Copyright © 2014 Elsevier Ltd. All rights reserved.
[Particle disease. Is tribology a topic in revision surgery?].
Elke, R
2001-05-01
To improve the longevity of endoprostheses, the main goal is to reduce wear. Polyethylene together with metal or ceramic is currently the most frequently used combination. Their clinical success is well documented in the literature. Many attempts to improve polyethylene in the past have failed. Materials successful in the laboratory have failed in clinical use. The most recent competitors of ultra-high molecular weight polyethylene (UHMWPE) are the highly cross-linked polyethylenes (HCLPE) and the hard-on-hard couplings such as metal-on-metal or ceramic-on-ceramic. Advantages and downsides regarding particle generation and higher standards of precision in positioning the components are discussed.
Preparation and characterizations of EGDE crosslinked chitosan electrospun membranes.
Aqil, A; Tchemtchoua, V T; Colige, A; Atanasova, G; Poumay, Y; Jérôme, C
2015-01-01
Composite Crosslinked nanofibrous membranes of chitosan, ethylene glycol diglycidyl ether (EGDE) and polyethylene oxide was successfully prepared with bead free morphology via electrospinning technique followed by heat mediated chemical crosslinking. Architectural stability of nanofiber mat in aqueous medium was achieved by chemical crosslinking of only 1% EGDE, and tensile strength tests revealed that increasing EGDE content has considerably enhance the elastic modulus of nanofibers. The structure, morphology and mechanical properties of nanofibers were characterized by Attenuated Total Reflection-Fourier Transform Infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM) and Instron machine, respectively. Skin fibroblasts and endothelial cells showed good attachment, proliferation and viability on crosslinked electrospun membranes. The results indicate a good biocompatibility and non-toxic nature of the resulted membrane.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Shepherd, D. V., E-mail: dvs23@cam.ac.uk; Shepherd, J. H.; Cameron, R. E.
We describe the production of collagen fibre bundles through a multi-strand, semi-continuous extrusion process. Cross-linking using an EDC (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide), NHS (N-hydroxysuccinimide) combination was considered. Atomic Force Microscopy and Raman spectroscopy focused on how cross-linking affected the collagen fibrillar structure. In the cross-linked fibres, a clear fibrillar structure comparable to native collagen was observed which was not observed in the non-cross-linked fibre. The amide III doublet in the Raman spectra provided additional evidence of alignment in the cross-linked fibres. Raman spectroscopy also indicated no residual polyethylene glycol (from the fibre forming buffer) or water in any of the fibres.
Kohsari, Iraj; Shariatinia, Zahra; Pourmortazavi, Seied Mahdi
2016-10-01
Antimicrobial chitosan-polyethylene oxide (CS-PEO) nanofiber mats loaded with 3, 5 and 10% (w/w) of zeolitic imidazolate framework-8 nanoparticles (ZIF-8 NPs, ∼60nm diameter) were developed by electrospinning technique. The CS-PEO-GA-3% ZIF-8 NPs crosslinked with glutaraldehyde (GA) vapor was also prepared. The electrospun mats were characterized by various analysis including FE-SEM, EDAX, elemental mapping, FT-IR, contact angle, TGA/DSC as well as tensile strength analysis. The nanofibers had average diameters within the range ∼70-120nm. Antimicrobial activities of the CS-PEO and CS-PEO-3% ZIF-8 mats were evaluated by the viable cell-counting method for determining their effectiveness in reducing or halting the growth of Staphylococcus aureus and Escherichia coli bacteria so that the CS-PEO mat containing 3% ZIF-8 revealed 100% bactericidal activity against both kinds of bacteria. The crosslinked CS-PEO-GA-3% ZIF-8 NPs sample was less thermally stable but more hydrophilic than its related non-crosslinked mat reflecting there was no need to crosslink the fibers using a chemical crosslinker having adverse effects. The highest hydrophobicity and appropriate thermal and tensile properties of CS-PEO-3% ZIF-8 NPs among those of the mats including 5 and 10% ZIF-8 NPs suggested that the mentioned mat is the most suitable sample for food coating applications. Copyright © 2016 Elsevier B.V. All rights reserved.
Kim, Jong Oh; Sahay, Gaurav; Kabanov, Alexander V; Bronich, Tatiana K
2010-04-12
Novel functional polymeric nanocarriers with ionic cores containing biodegradable cross-links were developed for delivery of chemotherapeutic agents. Block ionomer complexes (BIC) of poly(ethylene oxide)-b-poly(methacylic acid) (PEO-b-PMA) and divalent metal cations (Ca(2+)) were utilized as templates. Disulfide bonds were introduced into the ionic cores by using cystamine as a biodegradable cross-linker. The resulting cross-linked micelles with disulfide bonds represented soft, hydrogel-like nanospheres and demonstrated a time-dependent degradation in the conditions mimicking the intracellular reducing environment. The ionic character of the cores allowed to achieve a very high level of doxorubicin (DOX) loading (50% w/w) into the cross-linked micelles. DOX-loaded degradable cross-linked micelles exhibited more potent cytotoxicity against human A2780 ovarian carcinoma cells as compared to micellar formulations without disulfide linkages. These novel biodegradable cross-linked micelles are expected to be attractive candidates for delivery of anticancer drugs.
Jäger, Marcus; van Wasen, Andrea; Warwas, Sebastian; Landgraeber, Stefan; Haversath, Marcel; Group, VITAS
2014-01-01
Since polyethylene is one of the most frequently used biomaterials as a liner in total hip arthroplasty, strong efforts have been made to improve design and material properties over the last 50 years. Antioxidants seems to be a promising alternative to further increase durability and reduce polyethylene wear in long term. As of yet, only in vitro results are available. While they are promising, there is yet no clinical evidence that the new material shows these advantages in vivo. To answer the question if vitamin-E enhanced ultra-high molecular weight polyethylene (UHMWPE) is able to improve long-term survivorship of cementless total hip arthroplasty we initiated a randomized long-term multicenter trial. Designed as a superiority study, the oxidation index assessed in retrieval analyses of explanted liners was chosen as primary parameter. Radiographic results (wear rate, osteolysis, radiolucency) and functional outcome (Harris Hip Scores, University of California-Los Angeles, Hip Disability and Osteoarthritis Outcome Score, Visual Analogue Scale) will serve as secondary parameters. Patients with the indication for a cementless total hip arthroplasty will be asked to participate in the study and will be randomized to either receive a standard hip replacement with a highly cross-linked UHMWPE-X liner or a highly cross-linked vitamin-E supplemented UHMWPE-XE liner. The follow-up will be 15 years, with evaluation after 5, 10 and 15 years. The controlled randomized study has been designed to determine if Vitamin-E supplemented highly cross-linked polyethylene liners are superior to standard XLPE liners in cementless total hip arthroplasty. While several studies have been started to evaluate the influence of vitamin-E, most of them evaluate wear rates and functional results. The approach used for this multicenter study, to analyze the oxidation status of retrieved implants, should make it possible to directly evaluate the ageing process and development of the implant material itself over a time period of 15 years. PMID:25002933
[PREPARATION AND BIOCOMPATIBILITY OF IN SITU CROSSLINKING HYALURONIC ACID HYDROGEL].
Liang, Jiabi; Li, Jun; Wang, Ting; Liang, Yuhong; Zou, Xuenong; Zhou, Guangqian; Zhou, Zhiyu
2016-06-08
To fabricate in situ crosslinking hyaluronic acid hydrogel and evaluate its biocompatibility in vitro. The acrylic acid chloride and polyethylene glycol were added to prepare crosslinking agent polyethylene glycol acrylate (PEGDA), and the molecular structure of PEGDA was analyzed by Flourier transformation infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy. Hyaluronic acid hydrogel was chemically modified to prepare hyaluronic acid thiolation (HA-SH). And the degree of HA-SH was analyzed qualitatively and quantitatively by Ellman method. HA-SH solution in concentrations ( W/V ) of 0.5%, 1.0%, and 1.5% and PEGDA solution in concentrations ( W/V ) of 2%, 4%, and 6% were prepared with PBS. The two solutions were mixed in different ratios, and in situ crosslinking hyaluronic acid hydrogel was obtained; the crosslinking time was recorded. The cellular toxicity of in situ crosslinking hyaluronic acid hydrogel (1.5% HA-SH and 4% PEGDA mixed) was tested by L929 cells. Meanwhile, the biocompatibility of hydrogel was tested by co-cultured with human bone mesenchymal stem cells (hBMSCs). Flourier transformation infrared spectroscopy showed that most hydroxyl groups were replaced by acrylate groups; 1H nuclear magnetic resonance spectroscopy showed 3 characteristic peaks of hydrogen representing acrylate and olefinic bond at 5-7 ppm. The thiolation yield of HA-SH was 65.4%. In situ crosslinking time of hyaluronic acid hydrogel was 2 to 70 minutes in the PEGDA concentrations of 2%-6% and HA-SH concentrations of 0.5%-1.5%. The hyaluronic acid hydrogel appeared to be transparent. The toxicity grade of leaching solution of hydrogel was grade 1. hBMSCs grew well and distributed evenly in hydrogel with a very high viability. In situ crosslinking hyaluronic acid hydrogel has low cytotoxicity, good biocompatibility, and controllable crosslinking time, so it could be used as a potential tissue engineered scaffold or repairing material for tissue regeneration.
DFT Modeling of Cross-Linked Polyethylene: Role of Gold Atoms and Dispersion Interactions.
Blaško, Martin; Mach, Pavel; Antušek, Andrej; Urban, Miroslav
2018-02-08
Using DFT modeling, we analyze the concerted action of gold atoms and dispersion interactions in cross-linked polyethylene. Our model consists of two oligomer chains (PEn) with 7, 11, 15, 19, or 23 carbon atoms in each oligomer cross-linked with one to three Au atoms through C-Au-C bonds. In structures with a single gold atom the C-Au-C bond is located in the central position of the oligomer. Binding energies (BEs) with respect to two oligomer radical fragments and Au are as high as 362-489 kJ/mol depending on the length of the oligomer chain. When the dispersion contribution in PEn-Au-PEn oligomers is omitted, BE is almost independent of the number of carbon atoms, lying between 293 and 296 kJ/mol. The dispersion energy contributions to BEs in PEn-Au-PEn rise nearly linearly with the number of carbon atoms in the PEn chain. The carbon-carbon distance in the C-Au-C moiety is around 4.1 Å, similar to the bond distance between saturated closed shell chains in the polyethylene crystal. BEs of pure saturated closed shell PEn-PEn oligomers are 51-187 kJ/mol. Both Au atoms and dispersion interactions contribute considerably to the creation of nearly parallel chains of oligomers with reasonably high binding energies.
Design of a Papain Immobilized Antimicrobial Food Package with Curcumin as a Crosslinker
Sivakumar, Ponnurengam Malliappan; Doble, Mukesh
2015-01-01
Contamination of food products by spoilage and pathogenic microorganisms during post process handling is one of the major causes for food spoilage and food borne illnesses. The present green sustainable approach describes the covalent immobilization of papain to LDPE (low density polyethylene), HDPE (high density polyethylene), LLDPE (linear low density polyethylene) and PCL (polycaprolactam) with curcumin as the photocrosslinker. About 50% of curcumin and 82-92% of papain were successfully immobilized on these polymers. After 30 days, the free enzyme retained 87% of its original activity, while the immobilized enzyme retained more than 90% of its activity on these polymers. Papain crosslinked to LLDPE exhibited the best antibiofilm properties against Acinetobacter sp. KC119137.1 and Staphylococcus aureus NCIM 5021 when compared to the other three polymers, because of the highest amount of enzyme immobilized on this surface. Papain acts by damaging the cell membrane. The enzyme is able to reduce the amount of carbohydrate and protein contents in the biofilms formed by these organisms. Meat wrapped with the modified LDPE and stored at 4°C showed 9 log reduction of these organisms at the end of the seventh day when compared to samples wrapped with the bare polymer. This method of crosslinking can be used on polymers with or without functional groups and can be adopted to bind any type of antimicrobial agent. PMID:25906061
Huot, J Caitlin; Van Citters, Douglas W; Currier, John H; Currier, Barbara H; Mayor, Michael B; Collier, John P
2010-11-01
Posterior stabilized (PS) knee designs are a popular choice for cruciate sacrificing knee arthroplasty procedures. The introduction of PS inserts fabricated from highly cross-linked and remelted Ultra High Molecular Weight Polyethylene (UHMWPE) has recently generated concern as these materials have been shown to possess reduced mechanical properties. This study investigated whether highly cross-linked and remelted UHMWPE material (referred to as XRP) can be expected to perform similarly to historical gamma-air polyethylene, which has suffered few reported incidences of tibial post failure. Never-implanted gamma-air PS tibial inserts shelf-aged 14 years were examined and compared to XRP materials. Evaluation of oxidation levels, impact toughness, and fatigue strength demonstrated never-implanted gamma-air PS tibial inserts to possess nonuniform mechanical properties. Despite severe oxidation along the exterior of gamma-air tibial posts, comparatively low oxidation levels at the center of the tibial posts corresponded to sufficiently high mechanical properties. XRP material (75 kGy) showed superior impact toughness over shelf aged gamma-air material; however, tibial post fatigue testing demonstrated XRP material (100 kGy) to be less resistant to fatigue failure than historical gamma-air material. Results from this study indicate that XRP materials (100 kGy) may demonstrate an inferior resistance to tibial post failure than historical polyethylene. © 2010 Wiley Periodicals, Inc.
Partridge, Susan; Tipper, Joanne L; Al-Hajjar, Mazen; Isaac, Graham H; Fisher, John; Williams, Sophie
2018-05-01
Wear and fatigue of polyethylene acetabular cups have been reported to play a role in the failure of total hip replacements. Hip simulator testing under a wide range of clinically relevant loading conditions is important. Edge loading of hip replacements can occur following impingement under extreme activities and can also occur during normal gait, where there is an offset deficiency and/or joint laxity. This study evaluated a hip simulator method that assessed wear and damage in polyethylene acetabular liners that were subjected to edge loading. The liners tested to evaluate the method were a currently manufactured crosslinked polyethylene acetabular liner and an aged conventional polyethylene acetabular liner. The acetabular liners were tested for 5 million standard walking cycles and following this 5 million walking cycles with edge loading. Edge loading conditions represented a separation of the centers of rotation of the femoral head and the acetabular liner during the swing phase, leading to loading of the liner rim on heel strike. Rim damage and cracking was observed in the aged conventional polyethylene liner. Steady-state wear rates assessed gravimetrically were lower under edge loading compared to standard loading. This study supports previous clinical findings that edge loading may cause rim cracking in liners, where component positioning is suboptimal or where material degradation is present. The simulation method developed has the potential to be used in the future to test the effect of aging and different levels of severity of edge loading on a range of cross-linked polyethylene materials. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1456-1462, 2018. © 2017 Wiley Periodicals, Inc.
Teeter, Matthew G; Goyal, Prateek; Yuan, Xunhua; Howard, James L; Lanting, Brent A
2018-01-01
The purpose of this study is to measure acetabular cup position and wear of the highly crosslinked polyethylene liner in the supine and standing position for patients at a minimum of 10 years after the operation. A total of 38 patients were recruited at a mean of 12.5 years after the operation. All patients received a single acetabular cup design with a highly crosslinked liner and a 28-mm cobalt-chromium femoral head. Patients underwent supine and standing radiostereometric examinations in which the X-ray sources and detectors were positioned to obtain an anterior-posterior and cross-table lateral radiograph. Acetabular cup position and the three-dimensional wear rate were measured from the radiographs, and outcome scores were recorded for each patient. Anteversion significantly increased (P < .0001) a mean of 12° from supine (15.1° ± 10.4°) to standing (27.2° ± 10.5°) position. Inclination also significantly increased (P = .001) a mean of 2° from supine (44.4° ± 6.8°) to standing (46.3° ± 7.7°) position. There was no difference (P = .093) in wear rate between supine (0.067 ± 0.070 mm/y) and standing (0.073 ± 0.074 mm/y) positions. There were no correlations between cup orientation and wear rate in either position. Highly crosslinked polyethylene is a forgiving bearing material. Although adherence to the traditional acetabular position target zone is recommended, ensuring hip stability and consideration of the patient's functional position are also important objectives to consider for the acetabular position. Copyright © 2017 Elsevier Inc. All rights reserved.
Characteristics of highly cross-linked polyethylene wear debris in vivo
Baxter, Ryan M.; MacDonald, Daniel W.; Kurtz, Steven M.; Steinbeck, Marla J.
2014-01-01
Despite the widespread implementation of highly cross-linked polyethylene (HXLPE) liners to reduce the clinical incidence of osteolysis, it is not known if the improved wear resistance will outweigh the inflammatory potential of HXLPE wear debris generated in vivo. Thus, we asked: What are the differences in size, shape, number, and biological activity of polyethylene wear particles obtained from primary total hip arthroplasty revision surgery of conventional polyethylene (CPE) versus remelted or annealed HXLPE liners? Pseudocapsular tissue samples were collected from revision surgery of CPE and HXLPE (annealed and remelted) liners, and digested using nitric acid. The isolated polyethylene wear particles were evaluated using scanning electron microscopy. Tissues from both HXLPE cohorts contained an increased percentage of submicron particles compared to the CPE cohort. However, the total number of particles was lower for both HXLPE cohorts, as a result there was no significant difference in the volume fraction distribution and specific biological activity (SBA; the relative biological activity per unit volume) between cohorts. In contrast, based on the decreased size and number of HXLPE wear debris there was a significant decrease in total particle volume (mm3/g of tissue). Accordingly, when the SBA was normalized by total particle volume (mm3/gm tissue) or by component wear volume rate (mm3/year), functional biological activity of the HXLPE wear debris was significantly decreased compared to the CPE cohort. Indications for this study are that the osteolytic potential of wear debris generated by HXLPE liners in vivo is significantly reduced by improvements in polyethylene wear resistance. PMID:23436587
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ding Wanyu; Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Ministry of Education, Dalian University of Technology, Dalian 116024; Li Li
2013-03-14
The super-thin silicon oxynitride (SiO{sub x}N{sub y}) films were deposited onto the N doped polyethylene terephthalate (PET) surface. Varying the N doping parameters, the different chemical bond structures were obtained at the interface between the SiO{sub x}N{sub y} film and the PET surface. X-ray photoelectron spectra results showed that at the initial stage of SiO{sub x}N{sub y} film growth, the C=N bonds could be broken and C-N-Si crosslink bonds could be formed at the interface of SiO{sub x}N{sub y}/PET, which C=N bonds could be formed onto the PET surface during the N doping process. At these positions, the SiO{sub x}N{submore » y} film could be crosslinked well onto the PET surface. Meanwhile, the doped N could crosslink the [SiO{sub 4}] and [SiN{sub 4}] tetrahedrons, which could easily form the dense layer structure at the initial stage of SiO{sub x}N{sub y} film growth, instead of the ring and/or chain structures of [SiO{sub 4}] tetrahedrons crosslinked by O. Finally, from the point of applying SiO{sub x}N{sub y}/PET complex as the substrate, the present work reveals a simple way to crosslink them, as well as the crosslink model and physicochemical mechanism happened at the interface of complex.« less
Fully synthetic taped insulation cables
Forsyth, Eric B.; Muller, Albert C.
1984-01-01
A high voltage oil-impregnated electrical cable with fully polymer taped insulation operable to 765 kV. Biaxially oriented, specially processed, polyethylene, polybutene or polypropylene tape with an embossed pattern is wound in multiple layers over a conductive core with a permeable screen around the insulation. Conventional oil which closely matches the dielectric constant of the tape is used, and the cable can be impregnated after field installation because of its excellent impregnation characteristics.
On the use of doped polyethylene as an insulating material for HVDC cables
DOE Office of Scientific and Technical Information (OSTI.GOV)
Khalil, M.S.
1996-12-31
The merits of HVDC cables with polymeric insulation are well recognized. However, the development of such cables is still hampered due to the problems resulting from the complicated dependence of the electrical conductivity of the polymer on the temperature and the dc electric field and the effects of space charge accumulation in this material. Different methods have been suggested to solve these problems yet none of these methods seem to give a conclusive solution. The present report provides, firstly a critical review of the previous works reported in the literature concerning the development of HVDC cables with polymeric insulation. Differentmore » aspects of those works are examined and discussed. Secondly, an account is given on an investigation using low density polyethylene (LDPE) doped with an inorganic additive as a candidate insulating material for HVDC cables. Preliminary results from measurements of dc breakdown strength and insulation resistivity of both the undoped and the doped materials are presented. It is shown that the incorporation of an inorganic additive into LDPE has improved the performance of the doped material under polarity reversal dc conditions at room temperature. Moreover, the dependency of the insulation resistivity on temperature for the doped material appears to be beneficially modified.« less
Injectable dual redox responsive diselenide-containing poly(ethylene glycol) hydrogel.
Gong, Chu; Shan, Meng; Li, Bingqiang; Wu, Guolin
2017-09-01
An injectable dual redox responsive diselenide-containing poly(ethylene glycol) (PEG) hydrogel was successfully developed by combining the conceptions of injectable hydrogels and dual redox responsive diselenides. In the first step, four-armed PEG was modified with N-hydroxysuccinimide (NHS)-activated esters and thereafter, crosslinked by selenocystamine crosslinkers to form injectable hydrogels via the rapid reaction between NHS-activated esters and amino groups. The cross-sectional morphology, mechanical properties, and crosslinking modes of hydrogels were well characterized via scanning electron microscope (SEM), rheological measurements, and Fourier transform infrared spectra, respectively. In addition, the oxidation- and reduction-responsive degradation behaviors of hydrogels were observed and analyzed. The model drug, rhodamine B, was encapsulated in the hydrogel. The drug-loaded hydrogel exhibited a dual redox responsive release profile, which was consistent with the degradation experiments. The results of all experiments indicated that the formulated injectable dual redox responsive diselenide-containing PEG hydrogel can have potential applications in various biomedical fields such as drug delivery and stimuli-responsive drug release. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 2451-2460, 2017. © 2017 Wiley Periodicals, Inc.
Bonduelle, Colin V; Lau, Woon M; Gillies, Elizabeth R
2011-05-01
The functionalization of surfaces with poly(ethylene oxide) (PEO) is an effective means of imparting resistance to the adsorption of proteins and the attachment and growth of cells, properties that are critical for many biomedical applications. In this work, a new hyperthermal hydrogen induced cross-linking (HHIC) method was explored as a simple one-step approach for attaching PEO to surfaces through the selective cleavage of C-H bonds and subsequent cross-linking of the resulting carbon radicals. In order to study the effects of the process on the polymer, PEO-coated silicon wafers were prepared and the effects of different treatment times were investigated. Subsequently, using an optimized treatment time and a modified butyl polymer with increased affinity for PEO, the technique was applied to butyl rubber surfaces. All of the treated surfaces exhibited significantly reduced protein adsorption and cell growth relative to control surfaces and compared favorably with surfaces that were functionalized with PEO using conventional chemical methods. Thus HHIC is a simple and effective means of attaching PEO to non-functional polymer surfaces.
Wei, Weijia; Zhang, Xiujuan; Chen, Xianfeng; Zhou, Mengjiao; Xu, Ruirui; Zhang, Xiaohong
2016-04-21
Many drug molecules can be directly used as nanomedicine without the requirement of any inorganic or organic carriers such as silica and liposome nanostructures. This new type of carrier-free drug nanoparticles (NPs) has great potential in clinical treatment because of its ultra-high drug loading capacity and biodegradability. For practical applications, it is essential for such nanomedicine to possess robust stability and minimal premature release of therapeutic molecules during circulation in the blood stream. To meet this requirement, herein, we develop GSH-responsive and crosslinkable amphiphilic polyethylene glycol (PEG) molecules to modify carrier-free drug NPs. These PEG molecules can be cross-linked on the surface of the NPs to endow them with greater stability and the cross-link is sensitive to intracellular environment for bio-responsive drug release. With this elegant design, our experimental results show that the liberation of DOX from DOX-cross-linked PEG NPs is dramatically slower than that from DOX-non-cross-linked PEG NPs, and the DOX release profile can be controlled by tuning the concentration of the reducing agent to break the cross-link between PEG molecules. More importantly, in vivo studies reveal that the DOX-cross-linked PEG NPs exhibit favorable blood circulation half-life (>4 h) and intense accumulation in tumor areas, enabling effective anti-cancer therapy. We expect this work will provide a powerful strategy for stabilizing carrier-free nanomedicines and pave the way to their successful clinical applications in the future.
NASA Astrophysics Data System (ADS)
Suk, Jungdon; Lee, Yu Hwa; Kim, Do Youb; Kim, Dong Wook; Cho, Song Yun; Kim, Ji Man; Kang, Yongku
2016-12-01
We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 × 10-4 S cm-1), improved mechanical stability, and good electrochemical stability for all-solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 °C and 132 mAh/g at 0.5 °C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kurtulmus, Erhan; Karaboyacı, Mustafa; Yigitarslan, Sibel
2013-12-16
The pollution of polyethylene teraphtalate (PET) is in huge amounts due to the most widely usage as a packaging material in several industries. Regional pumice has several desirable characteristics such as porous structure, low-cost and light-weight. Considering the requirements approved by the Ministry of Public Works on isolation, composite insulation material consisting of PET and pumice was studied. Sheets of composites differing both in particle size of pumice and composition of polymer were produced by hot-molding technique. Characterization of new composite material was achieved by measuring its weight, density, flammability, endurance against both to common acids and bases, and tomore » a force applied, heat insulation and water adsorption capacity. The results of the study showed that produced composite material is an alternative building material due to its desirable characteristics; low weight, capability of low heat conduction.« less
EB-promoted recycling of waste tire rubber with polyolefins
NASA Astrophysics Data System (ADS)
Mészáros, László; Bárány, Tamás; Czvikovszky, Tibor
2012-09-01
Despite the fact that more and more methods and solutions are used in the recycling of polymers, there are still some problems, especially in the recycling of cross-linked materials such as rubber. Usually the biggest problem is the lack of compatibility between the cross-linked rubber and the thermoplastic matrix. In this study we applied ground tire rubber (GTR) as recycled material. The GTR was embedded into polyethylene (PE) and polyethylene/ethylene-vinyl acetate copolymer (PE/EVA) matrices. In order to increase the compatibility of the components electron beam (EB) irradiation was applied. The results showed that the irradiation has a beneficial effect on the polymer-GTR interfacial connection. The EB treatment increased not only the tensile strength but also the elongation at break. The irradiation had also positive effect on the impact strength properties.
Durability of crosslinked polydimethylsyloxanes: the case of composite insulators
NASA Astrophysics Data System (ADS)
Delor-Jestin, Florence; Tomer, Namrata S.; Pal Singh, Raj; Lacoste, Jacques
2008-04-01
Most applications of silicones are linked to their hydrophobic properties and (or) their high resistance to ageing (e.g. thermal ageing and photoageing). However, when placed in extreme environments, these materials can fail as in the case of epoxy/fiber glass composite powerlines insulators, where crosslinked polymethylsyloxanes (PDMSs) are used as the protective envelope (housing) of the insulator. We report on the behavior of both pure/noncrosslinked PDMSs and typical formulations used in industrial insulators, i.e. containing peroxide crosslinked PDMS, alumina trioxide hydrated (ATH) and silica. Special attention is paid on both (i) the sources of potential degradation and (ii) the best analytical methods that can be applied to the study of very complex formulations. (i) Aside from conventional types of ageing such as photo-ageing and thermal, hydrolytic, and service life ageings, treatments with acidic vapors, plasma and ozone possibly generating species from the reaction of a high electric field with air were also performed, which allowed to accelerate electrical and out-door ageings and to obtain differently aged materials. (ii) Aside from conventional analytical methods of polymer degradation such as FTIR/ATR spectroscopy and SEC, TG, hardness measurements, more specific methods like photo/DSC, TG/IR, thermoporosimetry, resistivity and density measurements were also performed to characterize the chemical and physical evolutions of polymer materials. In particular, it was found that treatment with nitric acid vapor has detrimental effects on the properties of both fire retardants (e.g. ATH) and PDMSs, affecting the hardness and resistivity of the formulated material.
Probe Into the Influence of Crosslinking on CO2 Permeation of Membranes
Li, Jinghui; Chen, Zhuo; Umar, Ahmad; Liu, Yang; Shang, Ying; Zhang, Xiaokai; Wang, Yao
2017-01-01
Crosslinking is an effective way to fabricate high-selective CO2 separation membranes because of its unique crosslinking framework. Thus, it is essentially significant to study the influence of crosslinking degree on the permeation selectivities of CO2. Herein, we report a successful and facile synthesis of a series of polyethylene oxide (PEO)-based diblock copolymers (BCP) incorporated with an unique UV-crosslinkable chalcone unit using Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) process. The membranes of as-prepared BCPs show superior carbon dioxide (CO2) separation properties as compared to nitrogen (N2) after UV-crosslinking. Importantly, the influence of different proportions of crosslinked chalcone on CO2 selectivities was systematically investigated, which revealed that CO2 selectivities increased obviously with the enhancement of chalcone fractions within a certain limit. Further, the CO2 selectivities of block copolymer with the best block proportion was studied by varying the crosslinking time which confirmed that the high crosslinking degree exhibited a better CO2/N2 (αCO2/N2) selectivities. A possible mechanism model revealing that the crosslinking degree played a key role in the gas separation process was also proposed. PMID:28051190
NASA Astrophysics Data System (ADS)
Chen, Jinhua; Asano, Masaharu; Yamaki, Tetsuya; Yoshida, Masaru
To develop a highly chemically stable polymer electrolyte membrane for application in a direct methanol fuel cell (DMFC), doubly crosslinked membranes were prepared by chemical crosslinking using bifunctional monomers, such as divinylbenzene (DVB) and bis(p, p-vinyl phenyl) ethane (BVPE), and by radiation crosslinking. The membranes were prepared by grafting of m, p-methylstyrene (MeSt) and p-tert-butylstyrene (tBuSt) into poly(ethylene- co-tetrafluoroethylene) (ETFE) films and subsequent sulfonation. The effects of the DVB and BVPE crosslinkers on the grafting kinetics and the properties of the prepared membranes, such as water uptake, proton conductivity and chemical stability were investigated. Radiation crosslinking was introduced by irradiation of the ETFE base film, the grafted film or the sulfonated membrane. The membrane crosslinked by DVB and BVPE crosslinkers and post-crosslinked by γ-ray irradiation of the corresponding grafted film possessed the highest chemical stability among the prepared membranes, a significantly lower methanol permeability compared to Nafion ® membranes, and a better DMFC performance for high methanol feed concentration. Therefore, this doubly crosslinked membrane was promising for application in a DMFC where relatively high methanol concentration could be fed.
Probe Into the Influence of Crosslinking on CO2 Permeation of Membranes
NASA Astrophysics Data System (ADS)
Li, Jinghui; Chen, Zhuo; Umar, Ahmad; Liu, Yang; Shang, Ying; Zhang, Xiaokai; Wang, Yao
2017-01-01
Crosslinking is an effective way to fabricate high-selective CO2 separation membranes because of its unique crosslinking framework. Thus, it is essentially significant to study the influence of crosslinking degree on the permeation selectivities of CO2. Herein, we report a successful and facile synthesis of a series of polyethylene oxide (PEO)-based diblock copolymers (BCP) incorporated with an unique UV-crosslinkable chalcone unit using Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) process. The membranes of as-prepared BCPs show superior carbon dioxide (CO2) separation properties as compared to nitrogen (N2) after UV-crosslinking. Importantly, the influence of different proportions of crosslinked chalcone on CO2 selectivities was systematically investigated, which revealed that CO2 selectivities increased obviously with the enhancement of chalcone fractions within a certain limit. Further, the CO2 selectivities of block copolymer with the best block proportion was studied by varying the crosslinking time which confirmed that the high crosslinking degree exhibited a better CO2/N2 (αCO2/N2) selectivities. A possible mechanism model revealing that the crosslinking degree played a key role in the gas separation process was also proposed.
Effect of crosslinking UHMWPE on its tensile and compressive creep performance.
Lewis, G; Carroll, M
2001-01-01
The in vitro quasi-static tensile and compressive creep properties of three sets of GUR 1050 ultra-high-molecular-weight polyethylene (UHMWPE) specimens were obtained. These sets were: control (as-received stock); "low-gamma" (specimens were crosslinked using gamma radiation, with a minimum dose of 5 Mrad); and "high-gamma" (specimens were crosslinked using gamma radiation, with a minimum dose of 15 Mrad). The % crystallinity (%C) and crosslink density (rho(x)) of the specimens in the three sets were also obtained. It was found that, in both tension and compression, crosslinking resulted in a significant depreciation in the creep properties, relative to control. The trend in the creep results is explained in terms of the impact of crosslinking on the polymer's %C and rho(x). The present results are in contrast to literature reports that show that crosslinking enhances the wear resistance of the polymer. The implications of the present results, taken together with the aforementioned literature results, are fully discussed vis-a-vis the use of crosslinked UHMWPE for fabricating articular components for arthroplasties.
NASA Astrophysics Data System (ADS)
Reinholds, Ingars; Kalkis, Valdis; Merijs-Meri, Remo; Zicans, Janis; Grigalovica, Agnese
2016-03-01
In this study, heat-shrinkable composites of electron beam irradiated high-density polyethylene (HDPE) composites with acrylonitrile-butadiene rubber (NBR) were investigated. HDPE/NBR blends at a ratio of components 100/0, 90/10, 80/20, 50/50 and 20/80 wt% were prepared using a two-roll mill. The compression molded films were irradiated high-energy (5 MeV) accelerated electrons up to irradiation absorbed doses of 100-300 kGy. The effect of electron beam induced cross-linking was evaluated by the changes of mechanical properties, gel content and by the differences of thermal properties, detected by differential scanning calorimetry. The thermo-shrinkage forces were determined as the kinetics of thermorelaxation and the residual shrinkage stresses of previously oriented (stretched up to 100% at above melting temperature of HDPE and followed by cooling to room temperature) specimens of irradiated HDPE/NBR blends under isometric heating-cooling mode. The compatibility between the both components was enhanced due to the formation of cross-linked sites at amorphous interphase. The results showed increase of mechanical stiffness of composites with increase of irradiation dose. The values of gel fraction compared to thermorelaxation stresses increased with the growth of irradiation dose level, as a result of formation cross-linked sites in amorphous PP/NBR interphase.
NASA Astrophysics Data System (ADS)
Shiryaeva, V. E.; Popova, T. P.; Korolev, A. A.; Kanat'eva, A. Yu.; Kurganov, A. A.
2017-08-01
New stationary phases for capillary columns in GC are synthesized and studied. The phases are prepared by depositing oligo(ethylene glycol)diacrylates on the column walls and subsequent polymerization (crosslinking) in the presence of peroxide initiators. It is shown that stationary phases based on monomers with molecular weights of 10 kDa or higher exhibit separation properties similar to those of conventional stationary phases based on polyethylene glycol (PEG); however, their thermal stability is higher because they have a higher degree of crosslinking and a more ordered structure of the crosslinked polymers than the respective parameters of phases based on native PEG.
NASA Astrophysics Data System (ADS)
Abolmaali, Samira Sadat; Tamaddon, Ali Mohammad; Dinarvand, Rasoul
2013-12-01
Soft polymeric nanomaterials were synthesized by the template-assisted method involving self-association of methoxy polyethylene glycol- g-branched polyethyleneimine (mPEG- g-branched PEI) ionomer by transition metal ions such as Zn2+ followed by chemical cross-linking of the polyamine core by dithiopropionic acid. The formation of donor-acceptor complexes of Zn2+ and PEI ionomer was characterized by FT-IR spectroscopy and potentiometric titration. Turbidimetry was performed to study the solution property of the complexes which depended on pH, relative weight fraction of mPEG, and the molar ratio of Zn2+. The cross-linking reaction was studied by TNBS assay, 1H-NMR, and size exclusion chromatography. Upon removal of Zn2+ from cl-mPEG- g-branched PEI/Zn2+ at pH 3 by dialysis, the resulting cross-linked self-assembly represented a uniform, stable, and less positively charged hydrogel-like nanosphere with an intensity-averaged size ranging from 150 to 250 nm as determined by a Zetasizer. Atomic forced microscopy imaging was performed in intermittent contact mode in air that revealed discrete and oval-to-spherically shaped particles with average sizes ranging from 40 to 50 nm depending on the degree of cross-linking. This functional nanocarrier is expected to exhibit some key features such as active encapsulation of negatively charged hydrophilic agents in the swollen core of polyamine network and a hydrophilic mPEG shell which provides an increased solubility and passive targeting of active pharmaceutical agents to impaired tissues. The nano-hydrogels especially at 12 % degrees of cross-link demonstrated excellent biocompatibility determined by different experiments such as albumin aggregation, erythrocyte aggregation, hemolysis, and MTT cytotoxicity assay. Moreover, biodegradability of the cross-links as shown by the Ellman assay can offer a time-dependent degradation and redox-stimulated release of active agents.
Zhang, Yumin; Zhou, Junhui; Yang, Cuihong; Wang, Weiwei; Chu, Liping; Huang, Fan; Liu, Qiang; Deng, Liandong; Kong, Deling; Liu, Jianfeng; Liu, Jinjian
2016-01-01
Although the shortcomings of small molecular antitumor drugs were efficiently improved by being entrapped into nanosized vehicles, premature drug release and insufficient tumor targeting demand innovative approaches that boost the stability and tumor responsiveness of drug-loaded nanocarriers. Here, we show the use of the core cross-linking method to generate a micelle with enhanced drug encapsulation ability and sensitivity of drug release in tumor. This kind of micelle could increase curcumin (Cur) delivery to HeLa cells in vitro and improve tumor accumulation in vivo. We designed and synthesized the core cross-linked micelle (CCM) with polyethylene glycol and folic acid-polyethylene glycol as the hydrophilic units, pyridyldisulfide as the cross-linkable and hydrophobic unit, and disulfide bond as the cross-linker. CCM showed spherical shape with a diameter of 91.2 nm by the characterization of dynamic light scattering and transmission electron microscope. Attributed to the core cross-linking, drug-loaded CCM displayed higher Nile Red or Cur-encapsulated stability and better sensitivity to glutathione than noncross-linked micelle (NCM). Cellular uptake and in vitro antitumor studies proved the enhanced endocytosis and better cytotoxicity of CCM-Cur against HeLa cells, which had a high level of glutathione. Meanwhile, the folate receptor-mediated drug delivery (FA-CCM-Cur) further enhanced the endocytosis and cytotoxicity. Ex vivo imaging studies showed that CCM-Cur and FA-CCM-Cur possessed higher tumor accumulation until 24 hours after injection. Concretely, FA-CCM-Cur exhibited the highest tumor accumulation with 1.7-fold of noncross-linked micelle Cur and 2.8-fold of free Cur. By combining cross-linking of the core with active tumor targeting of FA, we demonstrated a new and effective way to design nanocarriers for enhanced drug encapsulation, smart tumor responsiveness, and elevated tumor accumulation. PMID:27051287
Stambough, Jeffrey B.; Pashos, Gail; Bohnenkamp, Frank C.; Maloney, William J.; Martell, John M.; Clohisy, John C.
2016-01-01
Highly cross-linked polyethylene (HXLPE) is the most commonly used bearing surface in total hip arthroplasty (THA) because of its superior wear properties, but long-term results in young patients are limited. We report on the clinical outcome, radiographic wear patterns and survivorship of 72 patients ≤50 years old who had a 28-millimeter cobalt-chromium femoral head on HXLPE acetabular liner. Mean and median true linear wear rates at average ten-year follow-up were 0.0104 and 0.016 mm per year +/− 0.07 mm. Mean and median two-dimensional volumetric wear rates were 12.79 mm3 and 5.834 mm3 per year +/− 26.1mm3 as determined by Martell analysis. As a result of the minimal wear profile, there was no evidence of radiographic osteolysis and no wear-related revisions. PMID:26260785
Ast, Michael P; John, Thomas K; Labbisiere, Anthony; Robador, Nicolas; Valle, Alejandro Gonzalez Della
2014-06-01
Polyethylene liner fracture is a risk associated with the use of highly cross-linked UHMWPE. We performed a review of the voluntary reports of fractured liners to the US Food and Drug Administration to determine if any risk factors could be identified. There have been 74 reports of fractured Trilogy, Longevity liners to the US Food and Drug Administration since 1999. Most cases utilized small acetabular shells (≤54 mm) combined with large diameter heads (≥36 mm). Liners less than 7 mm thick at the weight bearing or 4.8 mm thick at the rim should be used with caution. At revision surgery, malpositioned shells should be revised and the use of a thin liner should be avoided. Copyright © 2014 Elsevier Inc. All rights reserved.
Oxidation resistant peroxide cross-linked UHMWPE produced by blending and surface diffusion
NASA Astrophysics Data System (ADS)
Gul, Rizwan M.; Oral, Ebru; Muratoglu, Orhun K.
2014-06-01
Ultra-high molecular weight polyethylene (UHMWPE) has been widely used as acetabular cup in total hip replacement (THR) and tibial component in total knee replacement (TKR). Crosslinking of UHMWPE has been successful used to improve its wear performance leading to longer life of orthopedic implants. Crosslinking can be performed by radiation or organic peroxides. Peroxide crosslinking is a convenient process as it does not require specialized equipment and the level of crosslinking can be manipulated by changing the amount of peroxide added. However, there is concern about the long-term stability of these materials due to possible presence of by-products. Vitamin E has been successfully used to promote long-term oxidative stability of UHMWPE. In this study, UHMWPE has been crosslinked using organic peroxide in the presence of Vitamin E to produce an oxidation resistant peroxide crosslinked material. Crosslinking was performed both in bulk by mixing peroxide and resin, and only on the surface using diffusion of peroxides.The results show that UHMWPE can be crosslinked using organic peroxides in the presence of vitamin E by both methods. However, the level of crosslinking decreases with the increase in vitamin E content. The wear resistance increases with the increase in crosslink density, and oxidation resistance significantly increases due to the presence of vitamin E.
Effect of thermal modification on rheological properties of polyethylene blends
DOE Office of Scientific and Technical Information (OSTI.GOV)
Siriprumpoonthum, Monchai; Nobukawa, Shogo; Yamaguchi, Masayuki, E-mail: m-yama@jaist.ac.jp
2014-03-15
We examined the effects of thermal modification under flow field on the rheological properties of linear low-density polyethylene (LLDPE) with high molecular weight, low-density polyethylene (LDPE), and their blends, without thermal stabilizer. Although structural changes during processing are not detected by size extrusion chromatography or nuclear magnetic resonance spectroscopy, linear viscoelastic properties changed greatly, especially for the LLDPE. A cross-linking reaction took place, leading to, presumably, star-shaped long-chain branches. Consequently, the modified LLDPE, having high zero-shear viscosity, became a thermorheologically complex melt. Moreover, it should be noted that the drawdown force, defined as the uniaxial elongational force at a constantmore » draw ratio, was significantly enhanced for the blends. Enhancement of elongational viscosity was also detected. The drawdown force and elongational viscosity are marked for the thermally modified blend as compared with those for the blend of thermally modified pure components. Intermolecular cross-linking reactions between LDPE and LLDPE, yielding polymers with more than two branch points per chain, result in marked strain-hardening in the elongational viscosity behavior even at small strain. The recovery curve of the oscillatory modulus after the shear modification is further evidence of a branched structure.« less
Li, Xianfeng; Murthy, N. Sanjeeva; Becker, Matthew L.; Latour, Robert A.
2016-01-01
A multiscale modeling approach is presented for the efficient construction of an equilibrated all-atom model of a cross-linked poly(ethylene glycol) (PEG)-based hydrogel using the all-atom polymer consistent force field (PCFF). The final equilibrated all-atom model was built with a systematic simulation toolset consisting of three consecutive parts: (1) building a global cross-linked PEG-chain network at experimentally determined cross-link density using an on-lattice Monte Carlo method based on the bond fluctuation model, (2) recovering the local molecular structure of the network by transitioning from the lattice model to an off-lattice coarse-grained (CG) model parameterized from PCFF, followed by equilibration using high performance molecular dynamics methods, and (3) recovering the atomistic structure of the network by reverse mapping from the equilibrated CG structure, hydrating the structure with explicitly represented water, followed by final equilibration using PCFF parameterization. The developed three-stage modeling approach has application to a wide range of other complex macromolecular hydrogel systems, including the integration of peptide, protein, and/or drug molecules as side-chains within the hydrogel network for the incorporation of bioactivity for tissue engineering, regenerative medicine, and drug delivery applications. PMID:27013229
Kosukegawa, Ima; Nagoya, Satoshi; Kaya, Mitsunori; Sasaki, Koichi; Sasaki, Mikito; Yamashita, Toshihiko
2011-09-01
We report a case with hypersensitivity to CoCr in total hip arthroplasty coupled with conventional polyethylene and CoCr femoral head. The patient complained of left hip pain and systemic fever, and computed tomography imaging revealed a periprosthetic cystic lesion, so we performed revision total hip arthroplasty using a titanium stem and ceramic head and highly crosslinked polyethylene. Hip pain and cystic lesion disappeared 3 years after revision surgery. Copyright © 2011 Elsevier Inc. All rights reserved.
NASA Technical Reports Server (NTRS)
Marsh, H. E., Jr.; Wallace, C. J.
1973-01-01
The removal of bile acids and cholesterol by polymeric absorption is discussed in terms of micelle-polymer interaction. The results obtained with a polymer composed of 75 parts PEO and 25 parts PB plus curing ingredients show an absorption of 305 to 309%, based on original polymer weight. Particle size effects on absorption rate are analyzed. It is concluded that crosslinked polyethylene oxide polymers will absorb water, crosslinked polybutadiene polymers will absorb lipids; neither polymer will absorb appreciable amounts of lipids from micellar solutions of lipids in water.
Small, porous polyacrylate beads
NASA Technical Reports Server (NTRS)
Yen, Shiao-Ping Siao (Inventor); Rembaum, Alan (Inventor); Dreyer, William J. (Inventor)
1976-01-01
Uniformly-shaped, porous, round beads are prepared by the co-polymerization of an acrylic monomer and a cross-linking agent in the presence of 0.05 to 5% by weight of an aqueous soluble polymer such as polyethylene oxide. Cross-linking proceeds at high temperature above about 50.degree.C or at a lower temperature with irradiation. Beads of even shape and even size distribution of less than 2 micron diameter are formed. The beads will find use as adsorbents in chromatography and as markers for studies of cell surface receptors.
Evaluation of pyrolysis and arc tracking on candidate wire insulation designs for space applications
NASA Astrophysics Data System (ADS)
Stueber, Thomas J.; Hammoud, Ahmad; Stavnes, Mark W.; Hrovat, Kenneth
1994-05-01
Polyimide wire insulation has been found to be vulnerable to pyrolization and arc tracking due to momentary short circuit arcing events. This report compares arc tracking susceptibility of candidate insulation configurations for space wiring applications. The insulation types studied in this report were gauge 20 (0.81 mm dia.) hybrid wiring constructions using polyimide, tetrafluoroethylene (TFE), cross-linked ethylene tetrafluoroethylene (XL-ETFE) and/or polytetrafluoroethylene (PTFE) insulations. These constructions were manufactured according to military wiring standards for aerospace applications. Arc track testing was conducted under DC bias and vacuum (10(exp -6) torr). The tests were conducted to compare the various insulation constructions in terms of their resistance to arc tracking restrike. The results of the tests are presented.
NASA Technical Reports Server (NTRS)
Morgan, Richard E. (Inventor); Meeks, Craig L. (Inventor)
2017-01-01
Insulation materials have a coating of a partially cured polymer on a plurality of fibers, and the plurality of coated fibers in a cross-linked polymeric matrix. Insulation may be formed by applying a preceramic polymer to a plurality of fibers, heating the preceramic polymer to form a partially cured polymer over at least portions of the plurality of fibers, disposing the plurality of fibers in a polymeric material, and curing the polymeric material. A rocket motor may be formed by disposing a plurality of coated fibers in an insulation precursor, curing the insulation precursor to form an insulation material without sintering the partially cured polymer, and providing an energetic material over the polymeric material. An article includes an insulation material over at least one surface.
Block copolymers for alkaline fuel cell membrane materials
NASA Astrophysics Data System (ADS)
Li, Yifan
Alkaline fuel cells (AFCs) using anion exchange membranes (AEMs) as electrolyte have recently received considerable attention. AFCs offer some advantages over proton exchange membrane fuel cells, including the potential of non-noble metal (e.g. nickel, silver) catalyst on the cathode, which can dramatically lower the fuel cell cost. The main drawback of traditional AFCs is the use of liquid electrolyte (e.g. aqueous potassium hydroxide), which can result in the formation of carbonate precipitates by reaction with carbon dioxide. AEMs with tethered cations can overcome the precipitates formed in traditional AFCs. Our current research focuses on developing different polymer systems (blend, block, grafted, and crosslinked polymers) in order to understand alkaline fuel cell membrane in many aspects and design optimized anion exchange membranes with better alkaline stability, mechanical integrity and ionic conductivity. A number of distinct materials have been produced and characterized. A polymer blend system comprised of poly(vinylbenzyl chloride)-b-polystyrene (PVBC-b-PS) diblock copolymer, prepared by nitroxide mediated polymerization (NMP), with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) or brominated PPO was studied for conversion into a blend membrane for AEM. The formation of a miscible blend matrix improved mechanical properties while maintaining high ionic conductivity through formation of phase separated ionic domains. Using anionic polymerization, a polyethylene based block copolymer was designed where the polyethylene-based block copolymer formed bicontinuous morphological structures to enhance the hydroxide conductivity (up to 94 mS/cm at 80 °C) while excellent mechanical properties (strain up to 205%) of the polyethylene block copolymer membrane was observed. A polymer system was designed and characterized with monomethoxy polyethylene glycol (mPEG) as a hydrophilic polymer grafted through substitution of pendent benzyl chloride groups of a PVBC-b-PS. The incorporation of the hydrophilic polymer allows for an investigation of the effect of hydration on ionic conductivity, resulting in the increase in membrane water affinity, enhancement of conductivity and reduced dependence of conductivity on relative humidity. A study of crosslinking of block copolymers was done wherein the crosslinking occurs in the non-matrix phase in order to maintain mechanical properties. The formation of a cationic crosslinked structure improves the mechanical integrity of the membrane in water while showing little deleterious effect on ionic conductivity and mechanical properties.
Photo-inducible Crosslinked Nanoassemblies for pH-Controlled Drug Release
Dickerson, Matthew; Winquist, Nickolas; Bae, Younsoo
2014-01-01
Purpose To control drug release from block copolymer nanoassemblies by variation in the degree of photo-crosslinking and inclusion of acid sensitive linkers. Methods Poly(ethylene glycol)-poly(aspartate-hydrazide-cinnamate) (PEG-CNM) block copolymers were prepared and conjugated with a model drug, doxorubicin (DOX), through acid sensitive hydrazone linkers. The block copolymers formed photo-inducible, self-assembled nanoassemblies (piSNAs), which were used to produce photo-inducible crosslinked nanoassemblies (piCNAs) through UV crosslinking. The nanoassemblies were characterized to determine particle size, surface charge, pH- and crosslinking-dependent DOX release, in vitro cytotoxicity, and intracellular uptake as a function of photo-crosslinking degree. Results Nanoassemblies with varying photo-crosslinking degrees were successfully prepared while retaining particle size and surface charge. Photo-crosslinking caused no noticeable change in DOX release from the nanoassemblies at pH 7.4, but the DOX-loaded nanoassemblies modulated drug release as a function of crosslinking at pH 6.0. The nanoassemblies showed similar cytotoxicity regardless of crosslinking degrees, presumably due to the low cellular uptake and cell nucleus drug accumulation. Conclusion Photo-crosslinking is useful to control drug release from pH-sensitive block copolymer nanoassemblies as a function of crosslinking without altering the particle properties, and thus providing unique tools to investigate the pharmaceutical effects of drug release on cellular response. PMID:24254196
Ethylene-Propylene Terpolymer Rubber Processing by Electron Beam Irradiation
NASA Astrophysics Data System (ADS)
Manaila, Elena N.; Zuga, Maria Daniela T.; Martin, Diana I.; Craciun, Gabriela D.; Ighigeanu, Daniel I.; Matei, Constantin I.
2007-04-01
The investigations on the cross-linking by accelerated electrons of 6.23 MeV in lowly unsaturated elastomers of EPDM (ethylene-propylene terpolymer rubber) type are presented. Two rubber blends based EPDM were prepared and irradiated at different doses up to 250kGy: blend A - based on EPDM maleinized with polyethylene, zinc oxide, plasticizers, filler, and blend B - based on EPDM / PE (50 % EPDM and 50% polyethylene). Blends were prepared on a laboratory electrically heated rubber mill at temperatures of 150-160°C to enable the polyethylene (PE) melting to be reached. Plates of 150 × 150 × 2 mm were obtained in a laboratory electrical press at 170°C.
Dielectric behavior of AC aged polyethylene in humid environment
DOE Office of Scientific and Technical Information (OSTI.GOV)
Scarpa, P.C.N.; Das-Gupta, D.K.; Bulinski, A.T.
1996-12-31
The present paper reports the results of a study of electrical aging of low density polyethylene (LDPE) aged in humid environment (0.1M NaCl) at an AC stress of 6kV/mm, 1kHz, at room temperature (RT) and at 65 C, and cross-linked polyethylene (XLPE) AC aged in humid environment (water) at an AC stress of 6kV/mm, 50Hz, at RT, for an extended period of time. For this study the dielectric spectroscopy data in the frequency range of 10{sup {minus}5}Hz to 10{sup 6}Hz and their comparative analysis, have been used to provide electrical analog models of the aging.
NASA Astrophysics Data System (ADS)
Bee, Soo-Tueen; Sin, Lee Tin; Ratnam, C. T.; Haraveen, K. J. S.; Tee, Tiam-Ting; Rahmat, A. R.
2015-10-01
In this study, the effects of electron beam irradiation on the properties of copper(II) oxide when added to low-density polyethylene (LDPE) blends were investigated. It was found that the addition of low loading level of copper(II) oxide (⩽2 phr) to LDPE results in significantly poorer gel content and hot set results. However, the incorporation of higher loading level of copper(II) oxide (⩾3 phr) could slightly increase the degree of crosslinking in all irradiated LDPE composites. This is due to the fact that higher amounts of copper(II) oxide could slightly induce the formation of free radicals in LDPE matrix. Besides, increasing irradiation doses was also found to gradually increase the gel content of LDPE composites by generating higher amounts of free radicals. As a consequence, these higher amounts of free radicals released in the LDPE matrix could significantly increase the degree of crosslinking. The addition of copper(II) oxide could reduce the tensile strength and fracture strain (elongation at break) of LDPE composites because of poorer interfacial adhesion effect between copper(II) oxide particles and LDPE matrix. Meanwhile, increasing irradiation doses on all copper(II) oxide added LDPE composites could marginally increase the tensile strength. In addition, increasing irradiation dose could enhance the thermal stability of LDPE composites by increasing the decomposition temperature. The oxidation induction time (OIT) analysis showed that, because of the crosslinking network in the copper(II) oxide added LDPE composites, oxidation reaction is much delayed.
Fernandes, Catarina G; Plácido, Diana; Lousa, Diana; Brito, José A; Isidro, Anabela; Soares, Cláudio M; Pohl, Jan; Carrondo, Maria A; Archer, Margarida; Henriques, Adriano O
2015-09-22
Transglutaminases are best known for their ability to catalyze protein cross-linking reactions that impart chemical and physical resilience to cellular structures. Here, we report the crystal structure and characterization of Tgl, a transglutaminase from the bacterium Bacillus subtilis. Tgl is produced during sporulation and cross-links the surface of the highly resilient spore. Tgl-like proteins are found only in spore-forming bacteria of the Bacillus and Clostridia classes, indicating an ancient origin. Tgl is a single-domain protein, produced in active form, and the smallest transglutaminase characterized to date. We show that Tgl is structurally similar to bacterial cell wall endopeptidases and has an NlpC/P60 catalytic core, thought to represent the ancestral unit of the cysteine protease fold. We show that Tgl functions through a unique partially redundant catalytic dyad formed by Cys116 and Glu187 or Glu115. Strikingly, the catalytic Cys is insulated within a hydrophobic tunnel that traverses the molecule from side to side. The lack of similarity of Tgl to other transglutaminases together with its small size suggests that an NlpC/P60 catalytic core and insulation of the active site during catalysis may be essential requirements for protein cross-linking.
Synthesis and Characterization of Poly(maleic Anhydride)s Cross-linked Polyimide Aerogels
NASA Technical Reports Server (NTRS)
Guo, Haiquan; Meador, Mary Ann B.
2015-01-01
With the development of technology for aerospace applications, new thermal insulation materials are required to be flexible and capable of surviving high heat flux. For instance, flexible insulation is needed for inflatable aerodynamic decelerators which are used to slow spacecraft for entry, descent and landing (EDL) operations. Polyimide aerogels have low density, high porosity, high surface area, and better mechanical properties than silica aerogels and can be made into flexible thin films, thus they are potential candidates for aerospace needs. The previously reported cross-linkers such as octa(aminophenyl)silsesquioxane (OAPS) and 1,3,5-triaminophenoxybenzene (TAB) are either expensive or not commercially available. Here, we report the synthesis of a series of polyimide aerogels cross-linked using various commercially available poly(maleic anhydride)s, as seen in Figure 1. The amine end capped polyimide oligomers were made with 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA) and diamine combinations of dimethylbenzidine (DMBZ) and 4, 4-oxydianiline (ODA). The resulting aerogels have low density (0.12 gcm3 to 0.16 gcm3), high porosity (90) and high surface area (380-554 m2g). The effect of the different poly(maleic anhydride) cross-linkers and polyimide backbone structures on density, shrinkage, porosity, surface area, mechanical properties, moisture resistance and thermal properties will be discussed.
NASA Astrophysics Data System (ADS)
Xie, Ansheng; Li, Shengtao; Zheng, Xiaoquan; Chen, George
2009-06-01
The statistical initiation and propagation characteristics of electrical trees in cross-linked polyethylene (XLPE) cables with different voltage ratings from 66 to 500 kV were investigated under a constant test voltage of 50 Hz/7 kV (the 66 kV rating cable is from UK, the others from China). It was found that the characteristics of electrical trees in the inner region of 66 kV cable insulation differed considerably from those in the outer region under the same test conditions; however, no significant differences appeared in the 110 kV rating cable and above. The initiation time of electrical trees in both the inner and the outer regions of the 66 kV cable is much shorter than that in higher voltage rating cables; in addition the growth rate of electrical trees in the 66 kV cable is much larger than that in the higher voltage rating cables. By using x-ray diffraction, differential scanning calorimetry and thermogravimetry methods, it was revealed that besides the extrusion process, the molecular weight of base polymer material and its distribution are the prime factors deciding the crystallization state. The crystallization state and the impurity content are responsible for the resistance to electrical trees. Furthermore, it was proposed that big spherulites will cooperate with high impurity content in enhancing the initiation and growth processes of electrical trees via the 'synergetic effect'. Finally, dense and small spherulites, high crystallinity, high purity level of base polymer material and super-clean production processes are desirable for higher voltage rating cables.
40 CFR 265.314 - Special requirements for bulk and containerized liquids.
Code of Federal Regulations, 2011 CFR
2011-07-01
... carbon (e.g., aluminosilicates, clays, smectites, Fuller's earth, bentonite, calcium bentonite... charcoal/activated carbon); or (ii) High molecular weight synthetic polymers (e.g., polyethylene, high..., polyisobutylene, ground synthetic rubber, cross-linked allylstyrene and tertiary butyl copolymers). This does not...
Hope, Natalie; Bellare, Anuj
2015-03-01
Ultrahigh-molecular-weight polyethylene (UHMWPE) is subjected to radiation crosslinking to form highly crosslinked polyethylene (HXLPE), which has improved wear resistance. First-generation HXLPE was subjected to thermal treatment to reduce or quench free radicals that can induce long-term oxidative degeneration. Most recently, antioxidants have been added to HXLPE to induce oxidative resistance rather than by thermal treatment. However, antioxidants can interfere with the efficiency of radiation crosslinking. We sought to identify (1) which antioxidant from among those tested (vitamin E, β-carotene, butylated hydroxytoluene, or pentaerythritol tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) causes the least reduction of crosslinking; (2) which promotes the greatest oxidative stability; and (3) which had the lowest ratio of oxidation index to crosslink density. Medical-grade polyethylene (PE) resin was blended with 0.1 weight % of the following stabilizers: alpha tocopherol (vitamin E), β-carotene, butylated hydroxytoluene (BHT), and pentaerythritol tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (a hindered phenol antioxidant [HPAO]). These blends were compression-molded into sheets and subjected to electron beam irradiation to a dose of 100 kGy. Equilibrium swelling experiments were conducted to calculate crosslink density. Each PE was subjected to accelerated aging for a period of 2 weeks and Fourier transform infrared spectroscopy was used to measure the maximum oxidation. Statistical analysis was conducted using analysis of variance with Fisher's protected least significant difference in which a p value of < 0.05 was used to define a significant difference. The least reduction of crosslinking in antioxidant-containing HXLPE was observed with HPAO, which had a crosslink density (n = 6) of 0.167 (effect size [ES] = 0.87; 95% confidence interval [CI], 0.162-0.173) mol/dm(3) compared with 0.139 (ES = 1.57; 95% CI, 0.132-0.146) mol/dm(3) (p = 0.020) for BHT, 0.131 (ES = 1.77; 95% CI, 0.123-0.139) mol/dm(3) (p = 0.004) for β-carotene, and 0.130 (ES = 1.79; 95% CI, 0.124-0.136) mol/dm(3) (p = 0.003) for vitamin E, whereas pure HXLPE had a crosslink density of 0.203 (95% CI, 0.170-0.235) mol/dm(3) (p = 0.005). BHT-PE had an oxidation index of 0.21 (ES = 13.14; 95% CI, 0.19-0.22) followed by HPAO-PE, vitamin E-PE and β-carotene-PE, which had oxidation indices of 0.28 (ES = 9.68; 95% CI, 0.28-0.29), 0.29 (ES = 9.59; 95% CI, 0.27-0.30), and 0.35 (ES = 6.68; 95% CI, 0.34-0.37), respectively (p < 0.001 for all groups). BHT-PE had the lowest ratio of oxidation index to crosslink density of the materials tested (1.49, ES = 1.94; 95% CI, 1.32-1.66) followed by HPAO-PE (1.70, ES = 1.52; 95% CI, 1.61-1.80), vitamin E-PE (2.21, ES = 0.52; 95% CI, 2.05-2.38), and β-carotene-PE (2.69, ES = -0.43; 95% CI, 2.46-2.93) compared with control PE (2.47, 95% CI, 2.07-2.88) with β-carotene (p = 0.208) and vitamin E (p = 0.129) not being different from the control. BHT-modified HXLPE was found in this study to have the lowest oxidation index as well as the lowest ratio of oxidation index to crosslink density compared with vitamin E, HPAO, and β-carotene-modified HXLPEs. More comprehensive studies are required such as wear testing using joint simulators as well as biocompatibility studies before BHT-modified HXLPE can be considered for clinical use. BHT is a synthetic antioxidant commonly used in the polymer industry to prevent long-term oxidative degradation and has been approved by the FDA for use in cosmetics and foodstuffs. It may be an attractive potential stabilizer for HXLPE in total joint replacements.
NASA Astrophysics Data System (ADS)
Wei, Weijia; Zhang, Xiujuan; Chen, Xianfeng; Zhou, Mengjiao; Xu, Ruirui; Zhang, Xiaohong
2016-04-01
Many drug molecules can be directly used as nanomedicine without the requirement of any inorganic or organic carriers such as silica and liposome nanostructures. This new type of carrier-free drug nanoparticles (NPs) has great potential in clinical treatment because of its ultra-high drug loading capacity and biodegradability. For practical applications, it is essential for such nanomedicine to possess robust stability and minimal premature release of therapeutic molecules during circulation in the blood stream. To meet this requirement, herein, we develop GSH-responsive and crosslinkable amphiphilic polyethylene glycol (PEG) molecules to modify carrier-free drug NPs. These PEG molecules can be cross-linked on the surface of the NPs to endow them with greater stability and the cross-link is sensitive to intracellular environment for bio-responsive drug release. With this elegant design, our experimental results show that the liberation of DOX from DOX-cross-linked PEG NPs is dramatically slower than that from DOX-non-cross-linked PEG NPs, and the DOX release profile can be controlled by tuning the concentration of the reducing agent to break the cross-link between PEG molecules. More importantly, in vivo studies reveal that the DOX-cross-linked PEG NPs exhibit favorable blood circulation half-life (>4 h) and intense accumulation in tumor areas, enabling effective anti-cancer therapy. We expect this work will provide a powerful strategy for stabilizing carrier-free nanomedicines and pave the way to their successful clinical applications in the future.Many drug molecules can be directly used as nanomedicine without the requirement of any inorganic or organic carriers such as silica and liposome nanostructures. This new type of carrier-free drug nanoparticles (NPs) has great potential in clinical treatment because of its ultra-high drug loading capacity and biodegradability. For practical applications, it is essential for such nanomedicine to possess robust stability and minimal premature release of therapeutic molecules during circulation in the blood stream. To meet this requirement, herein, we develop GSH-responsive and crosslinkable amphiphilic polyethylene glycol (PEG) molecules to modify carrier-free drug NPs. These PEG molecules can be cross-linked on the surface of the NPs to endow them with greater stability and the cross-link is sensitive to intracellular environment for bio-responsive drug release. With this elegant design, our experimental results show that the liberation of DOX from DOX-cross-linked PEG NPs is dramatically slower than that from DOX-non-cross-linked PEG NPs, and the DOX release profile can be controlled by tuning the concentration of the reducing agent to break the cross-link between PEG molecules. More importantly, in vivo studies reveal that the DOX-cross-linked PEG NPs exhibit favorable blood circulation half-life (>4 h) and intense accumulation in tumor areas, enabling effective anti-cancer therapy. We expect this work will provide a powerful strategy for stabilizing carrier-free nanomedicines and pave the way to their successful clinical applications in the future. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr09167e
Petis, Stephen M; Vasarhelyi, Edward M; Lanting, Brent A; Howard, James L; Naudie, Douglas D R; Somerville, Lyndsay E; McCalden, Richard W
2016-02-01
The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan-Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0-10.6) years for cobalt-chrome and 7.8 (range 2.1-10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%-97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%-99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%-98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%-99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up.
Choi, Dongkil; Lee, Woojin; Park, Jinwon; Koh, Wongun
2008-01-01
In this study, poly(ethylene glycol) (PEG)-based hydrogels having different network structures were synthesized by UV-initiated photopolymerization and used for the enzyme immobilization. PEGs with different molecular weight were acrylated by derivatizing both ends with acryloyl chloride and photopolymerization of PEG-diacrylate (PEG-DA) yielded crosslinked hydrogel network within 5 seconds. Attachment of acrylate groups and gelation were confirmed by ATR/FT-IR and FT-Raman spectroscopy. Network structures of hydrogels could be easily controlled by changing the molecular weight (MW) of PEG-DA and characterized by calculating molecular weight between crosslinks and mesh size from the swelling measurement. Synthesis of hydrogels with higher MW of PEG produced less crosslinked hydrogels having higher water content, larger value of Mc and mesh size, which resulted in enhanced mass transfer but loss of mechanical properties. For the enzyme immobilization, glucose oxidase (GOX) was immobilized inside PEG hydrogels by means of physical entrapment and covalent immobilization. Encapsulated GOX were covalently bound to PEG backbone using acryloyl-PEG-N-hydroxysuccinimide and maintained their activity over a week period without leakage. Kinetic study indicated that immobilized enzyme inside hydrogel prepared from higher MW of PEG possessed lower apparent Km (Michaelis-Menten constant) and higher activity.
Poursamar, S Ali; Lehner, Alexander N; Azami, Mahmoud; Ebrahimi-Barough, Somayeh; Samadikuchaksaraei, Ali; Antunes, A P M
2016-06-01
In this study porous gelatin scaffolds were prepared using in-situ gas foaming, and four crosslinking agents were used to determine a biocompatible and effective crosslinker that is suitable for such a method. Crosslinkers used in this study included: hexamethylene diisocyanate (HMDI), poly(ethylene glycol) diglycidyl ether (epoxy), glutaraldehyde (GTA), and genipin. The prepared porous structures were analyzed using Fourier Transform Infrared Spectroscopy (FT-IR), thermal and mechanical analysis as well as water absorption analysis. The microstructures of the prepared samples were analyzed using Scanning Electron Microscopy (SEM). The effects of the crosslinking agents were studied on the cytotoxicity of the porous structure indirectly using MTT analysis. The affinity of L929 mouse fibroblast cells for attachment on the scaffold surfaces was investigated by direct cell seeding and DAPI-staining technique. It was shown that while all of the studied crosslinking agents were capable of stabilizing prepared gelatin scaffolds, there are noticeable differences among physical and mechanical properties of samples based on the crosslinker type. Epoxy-crosslinked scaffolds showed a higher capacity for water absorption and more uniform microstructures than the rest of crosslinked samples, whereas genipin and GTA-crosslinked scaffolds demonstrated higher mechanical strength. Cytotoxicity analysis showed the superior biocompatibility of the naturally occurring genipin in comparison with other synthetic crosslinking agents, in particular relative to GTA-crosslinked samples. Copyright © 2016 Elsevier B.V. All rights reserved.
Products of Chemistry: Alkanes: Abundant, Pervasive, Important, and Essential.
ERIC Educational Resources Information Center
Seymour, Raymond B.
1989-01-01
Discusses the history and commercialization of alkanes. Examines the nomenclature and uses of alkanes. Studies polymerization and several types of polyethylenes: low-density, high-density, low-molecular-weight, cross-linked, linear low-density, and ultrahigh-molecular-weight. Includes a glossary of hydrocarbon terms. (MVL)
USDA-ARS?s Scientific Manuscript database
Ballistic delivery capability is essential to delivering vaccines and other therapeutics effectively to both livestock and wildlife in many global scenarios. Here, lyophilized poly(ethylene glycol) (PEG)-glycolide dimethacrylate crosslinked but degradable hydrogels were assessed as payload vehicles ...
Sillesen, Nanna H; Greene, Meridith E; Nebergall, Audrey K; Nielsen, Poul T; Laursen, Mogens B; Troelsen, Anders; Malchau, Henrik
2015-07-01
Vitamin E diffusion into highly cross-linked polyethylene (E-XLPE) is a method for enhancing oxidative stability of acetabular liners. The purpose of this study was to evaluate in vivo penetration of E-XLPE using radiostereometric analysis (RSA). Eighty-four hips were recruited into a prospective 10-year RSA. This is the first evaluation of the multicenter cohort after 3-years. All patients received E-XLPE liners (E1, Biomet) and porous-titanium coated cups (Regenerex, Biomet). There was no difference (P=0.450) in median femoral head penetration into the E-XLPE liners at 3-years comparing cobalt-chrome heads (-0.028mm; inter-quartile range (IQR) - 0.065 to 0.047) with ceramic heads (-0.043mm, IQR - 0.143to0.042). The 3-year follow-up indicates minimal E-XLPE liner penetration regardless of head material and minimal early cup movement. Copyright © 2015 Elsevier Inc. All rights reserved.
Stambough, Jeffrey B; Pashos, Gail; Bohnenkamp, Frank C; Maloney, William J; Martell, John M; Clohisy, John C
2016-01-01
Highly cross-linked polyethylene (HXLPE) is the most commonly used bearing surface in total hip arthroplasty (THA) because of its superior wear properties, but long-term results in young patients are limited. We report on the clinical outcome, radiographic wear patterns and survivorship of 72 patients ≤50 years old who had a 28-millimeter cobalt-chromium femoral head on HXLPE acetabular liner. Mean and median true linear wear rates at average ten-year follow-up were 0.0104 and 0.01 mm per year ± 0.07 mm. Mean and median two-dimensional volumetric wear rates were 12.79 mm(3) and 5.834 mm(3) per year ± 26.1mm(3) as determined by Martell analysis. As a result of the minimal wear profile, there was no evidence of radiographic osteolysis and no wear-related revisions. Copyright © 2016 Elsevier Inc. All rights reserved.
Self-assembling holographic biosensors and biocomputers.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Light, Yooli Kim; Bachand, George David; Schoeniger, Joseph S.
2006-05-01
We present concepts for self-assembly of diffractive optics with potential uses in biosensors and biocomputers. The simplest such optics, diffraction gratings, can potentially be made from chemically-stabilized microtubules migrating on nanopatterned tracks of the motor protein kinesin. We discuss the fabrication challenges involved in patterning sub-micron-scale structures with proteins that must be maintained in aqueous buffers to preserve their activity. A novel strategy is presented that employs dry contact printing onto glass-supported amino-silane monolayers of heterobifunctional crosslinkers, followed by solid-state reactions of these cross-linkers, to graft patterns of reactive groups onto the surface. Successive solution-phase addition of cysteine-mutant proteins andmore » amine-reactive polyethylene glycol allows assembly of features onto the printed patterns. We present data from initial experiments showing successful micro- and nanopatterning of lines of single-cysteine mutants of kinesin interleaved with lines of polyethylene, indicating that this strategy can be employed to arrays of features with resolutions suitable for gratings.« less
Extrudable polymer-polymer composites based on ultra-high molecular weight polyethylene
NASA Astrophysics Data System (ADS)
Panin, S. V.; Kornienko, L. A.; Alexenko, V. O.; Buslovich, D. G.; Dontsov, Yu. V.
2017-12-01
Mechanical and tribotechnical characteristics of polymer-polymeric composites of UHMWPE are studied with the aim of developing extrudable, wear-resistant, self-lubricant polymer mixtures for Additive Manufacturing (AM). The motivation of the study is their further application as feedstocks for 3D printing. Blends of UHMWPE with graft- and block copolymers of low-density polyethylene (HDPE-g-VTMS, HDPE-g-SMA, HDPE-b-EVA), polypropylene (PP), block copolymers of polypropylene and polyamide with linear low density polyethylene (PP-b-LLDPE, PA-b-LLDPE), as well as cross-linked polyethylene (PEX-b), are examined. The choice of compatible polymer components for an ultra- high molecular weight matrix for increasing processability (extrudability) is motivated by the search for commercially available and efficient additives aimed at developing wear-resistant extrudable polymer composites for additive manufacturing. The extrudability, mechanical properties and wear resistance of UHMWPE-based polymer-polymeric composites under sliding friction with different velocities and loads are studied.
Analysis of HEMCL Railgun Insulator Damage
2006-06-01
pyrolytic epoxy degradation and glass fiber softening and liquification in the insulator, it is determined that rail-to-rail plasmas are present behind...produces epoxy decomposition products in the form of gases, oils , waxes and chars solid (heavily cross-linked residues) [4]. The nature of the... pyrolytic decomposition product (wax) of the epoxy as in the fired specimens. Figures 6 and 7 are typical examples of glass fiber softening and
Guo, Limin; Chen, Zhilin; Lyu, Shaoyi; Fu, Feng; Wang, Siqun
2018-01-01
Cellulose nanofibril (CNF) aerogel is highly flammable and its mechanical strength is very soft, which is unfavourable due to safety concerns and impractical when used as the thermal insulation material. In this work, we used N-methylol dimethylphosphonopropionamide (MDPA) and 1,2,3,4-butanetetracarboxylic acid (BTCA) as co-additives and then prepared lightweight flame resistant CNF sponge-like aerogels via an eco-friendly freeze-drying and post cross-linking method. The CNF/BTCA/MDPA aerogel exhibited a better flame retardant performance, outstanding self-extinguishing behaviour and significantly increased char residue (by as much as 268%) compared with the neat CNF aerogel. Meanwhile, the resilience of the aerogel samples improved significantly as the flexibility decreased slightly. Furthermore, the aerogel samples still exhibited excellent thermal insulating properties with thermal conductivity as low as 0.03258W/(m k). The combination of these characteristics makes the CNF-based aerogel a promising insulation candidate for thermal protective equipment (e.g., fire-protection clothing or advanced spacesuit elements) in the future. Copyright © 2017 Elsevier Ltd. All rights reserved.
Shlar, Ilya; Droby, Samir; Rodov, Victor
2018-04-01
Bacterial contamination is a growing concern worldwide. The aim of this work was to develop an antimicrobial coating based on curcumin-cyclodextrin inclusion complex and using polyethylene terephthalate (PET) film as a support matrix. After a pre-treatment aimed to provide sufficient electric charge to the PET surface, it was electrostatically coated with repeated multilayers comprising alternately deposited positively-charged poly-l-lysine (PLL) and negatively-charged poly-l-glutamic acid (PLGA) and carboxymethyl-β-cyclodextrin (CMBCD). The coatings had an architecture (PLL-PLGA) 6 -(PLL-PLGA-PLL-CMBCD) n , with the number of repeated multilayers n varying from 5 to 20. The CMBCD molecules were either covalently cross-linked using carbodiimide crosslinker chemistry or left unbound. The surface morphology, structure and elemental composition of the coatings were analysed by scanning electron microscopy and energy dispersive x-ray spectroscopy. To impart antimicrobial properties to the coatings they were loaded with a natural phenolic compound curcumin forming inclusion complexes with β-cyclodextrin. The non-cross-linked coatings showed bactericidal activity towards Escherichia coli in the dark, and this activity was further enhanced upon illumination with white light. Curcumin was released from the non-cross-linked coatings into an aqueous medium in the form of cyclodextrin inclusion complex. After the cross-linking, the coating lost its dark antimicrobial activity but retained the photodynamic properties. Stabilized cross-linked curcumin-loaded coatings can serve a basis for developing photoactivated antimicrobial surfaces controlling bacterial contamination and spread. Copyright © 2018 Elsevier B.V. All rights reserved.
Simultaneous measurement of friction and wear in hip simulators.
Haider, Hani; Weisenburger, Joel N; Garvin, Kevin L
2016-05-01
We propose and have evaluated a method to measure hip friction during wear testing on a popular multi-station hip simulator. A 6-degree-of-freedom load cell underneath the specimen sensed forces and torques during implant wear testing of simulated walking. This included internal-external and adduction-abduction rotations which are often neglected during friction testing on pendulum-type machines. Robust mathematical analysis and data processing provided friction estimates in three simultaneous orthogonal rotations, over extended multi-million cycle wear tests. We tested various bearing couples including metal-on-plastic, ceramic-on-plastic, and metal-on-metal material couples. In one test series, new and intentionally scratched CoCrMo 40-mm-diameter femoral heads were tested against conventional ultrahigh-molecular-weight polyethylene, highly cross-linked, and highly cross-linked with vitamin E versions. The scratching significantly increased friction and doubled the wear of all groups. Before scratching, friction levels for the aforementioned plastic groups were 0.056 ± 0.0060, 0.062 ± 0.0080, and 0.070 ± 0.0045, respectively, but after scratching increased to 0.088 ± 0.018, 0.076 ± 0.0066, and 0.082 ± 0.0049, respectively, all statistically significant increases (p = 0.00059, 0.00005, 0.0115, respectively). In another test series of 44-mm femoral head diameter hips, metal-on-plastic hips with conventional ultrahigh-molecular-weight polyethylene showed the lowest friction at 0.045 ± 0.0085, followed by highly cross-linked with 0.046 ± 0.0035 (not significantly different). In a ceramic-on-plastic design with conventional ultrahigh-molecular-weight polyethylene, higher friction 0.079 ± 0.0070 was measured likely due to that ceramic surface being rougher than usual. Metal-on-metal hips were compared without and with a TiN coating, resulting in 0.049 ± 0.014 and 0.097 ± 0.020 friction factors, respectively (statistically significant, p < 0.001), and the coating wore away on all coated hips eventually. Higher friction mostly correlated with higher wear or damage to femoral heads or implant coatings, except for the highly cross-linked wear resistant ultrahigh-molecular-weight polyethylene which had slightly higher friction, confirming the same finding in other independent studies. This type of friction measurements can help screen for clamping and elevated wear of metal-on-metal and resurfacing total hip replacements, surgical malpositioning, and abraded and otherwise damaged surfaces. © IMechE 2016.
Powder Production From Waste Polyethylene Terephthalate (PET) Water Bottles
2014-06-01
10 5. References 1. Van Brederode, R. A.; Steinkamp, R. A. Crosslinkable Polymer Powder and Laminate . U.S. Patent 42256560A, 1980, http...16. Parquette, B.; Giri, A.; Daniel, J.; O’Brien,D. J.; Brennan,S.; Cho, K.; Tzeng, J. Cryomilling of Thermoplastic Powder for Prepreg Applications
Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene
Lane, J. Matthew; Moore, Nathan W.
2018-02-01
Thermal degradation of polyethylene is studied under the extremely high rate temperature ramps expected in laser-driven and X-ray ablation experiments—from 10 10 to 10 14 K/s in isochoric, condensed phases. The molecular evolution and macroscopic state variables are extracted as a function of density from reactive molecular dynamics simulations using the ReaxFF potential. The enthalpy, dissociation onset temperature, bond evolution, and observed cross-linking are shown to be rate dependent. These results are used to parametrize a kinetic rate model for the decomposition and coalescence of hydrocarbons as a function of temperature, temperature ramp rate, and density. In conclusion, the resultsmore » are contrasted to first-order random-scission macrokinetic models often assumed for pyrolysis of linear polyethylene under ambient conditions.« less
Bellare, Anuj; Bistolfi, Alessandro
2017-01-01
Ultra-high molecular weight polyethylene (UHMWPE) is the most common bearing material in total joint arthroplasty due to its unique combination of superior mechanical properties and wear resistance over other polymers. A great deal of research in recent decades has focused on further improving its performances, in order to provide durable implants in young and active patients. From “historical”, gamma-air sterilized polyethylenes, to the so-called first and second generation of highly crosslinked materials, a variety of different formulations have progressively appeared in the market. This paper reviews the structure–properties relationship of these materials, with a particular emphasis on the in vitro and in vivo wear performances, through an analysis of the existing literature. PMID:28773153
Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lane, J. Matthew; Moore, Nathan W.
Thermal degradation of polyethylene is studied under the extremely high rate temperature ramps expected in laser-driven and X-ray ablation experiments—from 10 10 to 10 14 K/s in isochoric, condensed phases. The molecular evolution and macroscopic state variables are extracted as a function of density from reactive molecular dynamics simulations using the ReaxFF potential. The enthalpy, dissociation onset temperature, bond evolution, and observed cross-linking are shown to be rate dependent. These results are used to parametrize a kinetic rate model for the decomposition and coalescence of hydrocarbons as a function of temperature, temperature ramp rate, and density. In conclusion, the resultsmore » are contrasted to first-order random-scission macrokinetic models often assumed for pyrolysis of linear polyethylene under ambient conditions.« less
Magnetically responsive enzyme powders
NASA Astrophysics Data System (ADS)
Pospiskova, Kristyna; Safarik, Ivo
2015-04-01
Powdered enzymes were transformed into their insoluble magnetic derivatives retaining their catalytic activity. Enzyme powders (e.g., trypsin and lipase) were suspended in various liquid media not allowing their solubilization (e.g., saturated ammonium sulfate and highly concentrated polyethylene glycol solutions, ethanol, methanol, 2-propanol) and subsequently cross-linked with glutaraldehyde. Magnetic modification was successfully performed at low temperature in a freezer (-20 °C) using magnetic iron oxides nano- and microparticles prepared by microwave-assisted synthesis from ferrous sulfate. Magnetized cross-linked enzyme powders were stable at least for two months in water suspension without leakage of fixed magnetic particles. Operational stability of magnetically responsive enzymes during eight repeated reaction cycles was generally without loss of enzyme activity. Separation of magnetically modified cross-linked powdered enzymes from reaction mixtures was significantly simplified due to their magnetic properties.
A novel preparation of milk protein/polyethylene terephthalate fabric
NASA Astrophysics Data System (ADS)
Zhou, J. F.; Zheng, D. D.; Zhong, L.; Zhang, F. X.; Zhang, G. X.
2016-07-01
In this work, -NH2 groups were introduced to polyethylene terephthalate (PET) fibers by nitration and reduction method, and then milk protein was grafted on the nitrated and reduced PET (NR PET) fibers by sucrose glycidyl ether crosslinking agent. FTIR suggested the milk protein was successfully grafted on PET fiber surface. SEM images showed a layer of substance covered on the PET fiber surface. DSC demonstrated an excellent thermal stability of milk protein/PET fiber. The moisture regain was improved by milk protein/PET fiber. Moreover, the crease recovery angle and stiffness were retained by the milk protein/PET fabric.
E-Beam Processing of Polymer Matrix Composites for Multifunctional Radiation Shielding
NASA Technical Reports Server (NTRS)
Hou, Tan-Hung; Wilson, John W.; Jensen, Brian J.; Thibeault, Sheila A.; Chang, Chie K.; Kiefer, Richard L.
2005-01-01
Aliphatic polymers were identified as optimum radiation shielding polymeric materials for building multifunctional structural elements for in-space habitats. Conceptual damage tolerant configurations of polyolefins have been proposed, but many manufacturing issues relied on methods and materials which have sub-optimal radiation shielding characteristics (for example, epoxy matrix and adhesives). In the present approach, we shall investigate e-beam processing technologies for inclusion of high-strength aliphatic polymer reinforcement structures into a highly cross-linked polyolefin matrix. This paper reports the baseline thermo-mechanical properties of low density polyethylene and highly crystallized polyethylene.
Tamura, Masato; Yanagawa, Fumiki; Sugiura, Shinji; Takagi, Toshiyuki; Sumaru, Kimio; Kanamori, Toshiyuki
2015-01-01
This paper describes the generation of “click-crosslinkable“ and “photodegaradable“ gelatin hydrogels from the reaction between dibenzocycloctyl-terminated photoclevable tetra-arm polyethylene glycol and azide-modified gelatin. The hydrogels were formed in 30 min through the click-crosslinking reaction. The micropatterned features in the hydrogels were created by micropatterned light irradiation; the minimum resolution of micropatterning was 10-μm widths for line patterns and 20-μm diameters for circle patterns. Cells were successfully encapsulated in the hydrogels without any loss of viability across a wide concentration range of crosslinker. In contrast, an activated-ester-type photocleavable crosslinker, which we previously used to prepare photodegradable gelatin hydrogels, induced a decrease in cell viability at crosslinker concentrations greater than 1.8 mM. We also observed morphology alteration and better growth of cancer cells in the click-crosslinked photodegradable gelatin hydrogels that included matrigel than in the absence of matrigel. We also demonstrated micropatterning of the hydrogels encapsulating cells and optical cell separation. Both of the cells that remained in the non-irradiated area and the cells collected from the irradiated area maintained their viability. PMID:26450015
Effect of Cross-Linking on Free Volume Properties of PEG Based Thiol-Ene Networks
NASA Astrophysics Data System (ADS)
Ramakrishnan, Ramesh; Vasagar, Vivek; Nazarenko, Sergei
According to the Fox and Loshaek theory, in elastomeric networks, free volume decreases linearly with the cross-link density increase. The aim of this study is to show whether the poly(ethylene glycol) (PEG) based multicomponent thiol-ene elastomeric networks demonstrate this model behavior? Networks with a broad cross-link density range were prepared by changing the ratio of the trithiol crosslinker to PEG dithiol and then UV cured with PEG diene while maintaining 1:1 thiol:ene stoichiometry. Pressure-volume-temperature (PVT) data of the networks was generated from the high pressure dilatometry experiments which was fit using the Simha-Somcynsky Equation-of-State analysis to obtain the fractional free volume of the networks. Using Positron Annihilation Lifetime Spectroscopy (PALS) analysis, the average free volume hole size of the networks was also quantified. The fractional free volume and the average free volume hole size showed a linear change with the cross-link density confirming that the Fox and Loshaek theory can be applied to this multicomponent system. Gas diffusivities of the networks showed a good correlation with free volume. A free volume based model was developed to describe the gas diffusivity trends as a function of cross-link density.
NASA Astrophysics Data System (ADS)
Wang, Jingjing; Wei, Jun
2016-09-01
Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.
Lee, Hyun Jin; Bae, Younsoo
2011-07-11
Block copolymer cross-linked nanoassemblies (CNAs) were developed as stable supramolecular templates for particulate drug delivery. Poly(ethylene glycol)-poly(aspartate) [PEG-p(Asp)] block copolymers, consisting of PEG (5 or 12 kDa) and Asp (5, 14, 25, 33, and 37 repeating units), were used as scaffolds and grafts in combination to prepare a nanoassembly library of grafted nanoassemblies (GNAs) and CNAs. Four synthesis routes were tested to maximize the number of drug-binding Asp units per nanoassembly. Grafting-onto-scaffold and grafting-from-scaffold methods were used for GNA synthesis. Either partially or completely deprotected PEG-p(Asp) was cross-linked with diamine compounds to prepare CNAs. (1)H NMR and GPC measurements showed that GNAs and CNAs contained the maximum 183 and 253 Asp units, respectively. Initial screening of the nanoassemblies revealed that GNAs would be impractical for further development as drug carriers due to variable grafting efficiency and low product yields. CNAs were obtained in high yields and identified as a promising supramolecular template that can entrap and release ionizable drugs (doxorubicin), enhancing the particle stability of nanoassemblies in the pharmaceutically relevant pH ranges between 4 and 9. Light scattering measurements demonstrated that the particle size of CNAs remained uniform before and after drug entrapment, causing neither aggregation nor dissociation (<5 mg/mL).
Tsukamoto, Manabu; Mori, Toshiharu; Ohnishi, Hideo; Uchida, Soshi; Sakai, Akinori
2017-12-01
A number of studies on total hip arthroplasty have compared highly cross-linked polyethylene (HXLPE) with conventional polyethylene (CPE) liners beyond 10 years. However, the impact of HXLPE on the wear-related reoperation rate is unclear. The purpose of this study was to evaluate the clinical advantage of using a single manufacturer's HXLPE in terms of reducing the reoperation rate. The study was a follow-up retrospective cohort study over a mean of 12 years that examined patients aged 45-70 years with cementless total hip arthroplasty using a 26-mm-diameter cobalt-chromium head. Sixty-seven patients (79 hips; HXLPE group = 41 hips, CPE group = 38 hips) were evaluated for a minimum 10-year follow-up. Kaplan-Meier survival analysis was performed, with wear-related reoperations and radiographic osteolysis serving as the end points. The polyethylene wear rate was also assessed. The mean 12-year follow-up rates of survivorship that were evaluated using wear-related reoperations as the end point were 100% and 91.4% in the HXLPE and CPE groups, respectively (P = .007), and the mean 12-year follow-up rates of survivorship with osteolysis as the end point were 100% and 36.2%, respectively (P < .001). Compared with the CPE group, the HXLPE group presented a significantly reduced wear rate (HXLPE group, 0.035 mm/y; CPE group, 0.118 mm/y). A unique strength of this study is that we assessed a single manufacturer's HXLPE while keeping most other implant parameters uniform. This study reveals the clinical advantage of using a single manufacturer's HXLPE in terms of a reduced wear-related reoperation rate at a mean 12-year follow-up. Copyright © 2017 Elsevier Inc. All rights reserved.
Influence of heat treatment on structural, mechanical and wear properties of crosslinked UHMWPE.
Chiesa, R; Moscatelli, M; Giordano, C; Siccardi, F; Cigada, A
2004-01-01
New crosslinked ultra high molecular weight polyethylenes (UHMWPEs) have recently been developed, characterized and introduced in clinical applications. UHMWPE cross-linking treatments are very promising for reducing osteolysis induced by wear debris. The irradiation type, gamma or beta, the dosage and the thermal treatment performed during or following the irradiation process are all factors affecting polyethylene wear resistance. Thermal stabilization treatments performed after or during the irradiation process at a temperature above melting point (i.e. >130 degrees C) have been proven to effectively remove the free radicals generated during irradiation from UHMWPE, but their effect on the mechanical properties of UHMWPE are not completely clear. In addition to wear rate reduction, maintaining good mechanical properties is fundamental aspect in designing the new generation of crosslinked UHMWPE for artificial load bearing materials, especially considering the application in total knee replacements. In this study, we investigated the influence of different stabilization treatments, performed after gamma irradiation, on structural, wear and mechanical properties of UHMWPE. We performed four different stabilization treatments, with different temperatures and cooling rates, on 100 kGy gamma irradiated UHMWPE. Structural properties of UHMWPE were assessed by differential scanning calorimetry (DSC). To assess the mechanical performance of the materials, uni-axial tensile tests were performed according to the ASTM D638 standard, bi-axial tension performance was evaluated by small punch tests (ASTM F2183-02), toughness resistance was evaluated by the Izod method (ASTM F648), and cold flow resistance was analysed by a dynamic compressive test. Evaluation of wear resistance was by a multidirectional pin-on-disk screening machine. Materials considered were in "aged" and "non-aged" conditions. Results confirmed that cross-linking greatly enhances UHMWPE wear resistance, but introduces some detrimental effects on the mechanical properties. In this study, we found that the negative ef-fects on the mechanical properties of crosslinked UHMWPE can be modulated, to some extent, by choosing a thermal stabiliza-tion treatment at a correct temperature and cooling rate. (Journal of Applied Biomaterials & Biomechanics 2004; 2: 20-8).
NASA Astrophysics Data System (ADS)
Reinitz, Steven D.
Ultra-high molecular weight polyethylene (UHMWPE) remains the most common bearing material for total joint arthroplasty. Advances in radiation cross-linking and other post-consolidation treatments have led to a rapid differentiation of polyethylene products on the market, with more than twenty unique materials currently being sold by the five largest orthopaedic manufacturers alone. Through oxidation, cross-link density, and free radical measurements, this work demonstrates for the first time that in vivo material degradation is occurring in cross-linked UHMWPE materials. Based on the rate of the reaction in certain materials, it is concluded that oxidative degradation may compromise the mechanical properties of the bearings in as few as ten years, potentially leading to early clinical failure of the devices. Using the knowledge gained from this work as well as previously published observations about UHMWPE oxidation, a two-mechanism model of oxidation is proposed that offers an explanation for the observed in vivo changes. From this model it is concluded that oxidative degradation is in part the result of in vivo chemical species. The two-mechanism model of oxidation suggests that different processing techniques for UHMWPE may reduce the risk of oxidative degradation. It is concluded that by avoiding any radiation cross-linking step, Equal Channel Angular Processing (ECAP) can produce UHMWPE materials with a reduced risk for in vivo oxidation while at the same time offering superior mechanical properties compared to commercially available UHMWPE materials, as well as similar wear behavior. Using dynamic mechanical analysis, the entanglement density in ECAP materials is quantified, and is related back to the ECAP processing parameters. The relationship between entanglement density and resultant material properties is established. The results will allow informed processing parameter selection for producing optimized materials for orthopaedics and other applications.
Takahashi, Yasuhito; Tateiwa, Toshiyuki; Shishido, Takaaki; Masaoka, Toshinori; Kubo, Kosuke; Yamamoto, Kengo
2016-10-01
The in-vivo progression of creep and wear in ultra-high molecular weight polyethylene (UHMWPE) acetabular liners has been clinically evaluated by measuring radiographic penetration of femoral heads. In such clinical assessments, however, viscoelastic strain relaxation has been rarely considered after a removal of hip joint loading, potentially leading to an underestimation of the penetrated thickness. The objective of this study was to investigate shape-recovery behavior of pre-compressed, radiation crosslinked and antioxidant vitamin E-diffused UHMWPE acetabular liners, and also to characterize the effects of varying their internal diameter (ID) and wall thickness (WT). We applied uniaxial compression to the UHMWPE specimens of various ID (28, 32, 36mm) and WT (4.8, 6.8, 8.9mm) for 4320min under the constant load of 3000N, and subsequently monitored the strain-relaxation behavior as a function of time after unloading. It was observed that there was a considerable shape recovery of the components after removal of the external static load. Reducing ID and WT significantly accelerated the rate of creep strain recovery, and varying WT was more sensitive to the recovery behavior than ID. Creep deformation of the tested liners recovered mostly within the first 300min after unloading. Note that approximately half of the total recovery amount proceeded just within 5min after unloading. These results suggest a remarkably high capability of shape recovery of vitamin E-diffused highly crosslinked UHMWPE. In conclusion, the time-dependent shape recovering and the diameter-thickness effect on its behavior should be carefully considered when the postoperative penetration is quantified in highly crosslinked UHMWPE acetabular liners (especially on the non-weight bearing radiographs). Copyright © 2016 Elsevier Ltd. All rights reserved.
Matsumoto, Mayuko; Terashima, Takaya; Matsumoto, Kazuma; Takenaka, Mikihito; Sawamoto, Mitsuo
2017-05-31
Orthogonal self-assembly and intramolecular cross-linking of amphiphilic random block copolymers in water afforded an approach to tailor-make well-defined compartments and domains in single polymer chains and nanoaggregates. For a double compartment single-chain polymer, an amphiphilic random block copolymer bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dodecyl, benzyl, and olefin pendants was synthesized by living radical polymerization (LRP) and postfunctionalization; the dodecyl and benzyl units were incorporated into the different block segments, whereas PEG pendants were statistically attached along a chain. The copolymer self-folded via the orthogonal self-assembly of hydrophobic dodecyl and benzyl pendants in water, followed by intramolecular cross-linking, to form a single-chain polymer carrying double yet distinct hydrophobic nanocompartments. A single-chain cross-linked polymer with a chlorine terminal served as a globular macroinitiator for LRP to provide an amphiphilic tadpole macromolecule comprising a hydrophilic nanoparticle and a hydrophobic polymer tail; the tadpole thus self-assembled into multicompartment aggregates in water.
NASA Astrophysics Data System (ADS)
Barba, Bin Jeremiah D.; Aranilla, Charito T.; Relleve, Lorna S.; Cruz, Veriza Rita C.; Vista, Jeanina Richelle; Abad, Lucille V.
2018-03-01
Uncontrolled hemorrhage remains a persistent problem especially in anatomical areas where compression and tourniquet cannot be applied. Hemostatic agents are materials which can achieve control of bleeding in acute, life-threatening traumatic coagulopathy. In this study, we prepared biocompatible hydrogel-based hemostat crosslinked by ionizing radiation. Granules made from carboxymethyl cellulose and dressing from kappa carrageenan and polyethylene oxide were characterized by FT-IR, SEM, and gel analysis. Gamma radiation with a dose of 25 kGy was used for sterilization process. Stability studies indicate that the products remain effective with a shelf life of up to 18 months based on accelerated aging. Both hemostatic agents were demonstrated to be effective in vitro blood clotting assays showing a low blood clotting index, high platelet adhesion capacity and accelerated clotting time. Hemostat granules and dressing were also used in a femoral artery rat bleeding model where hemorrhage control was achieved in 90 s without compression and resulted in 100% survival rate after a 7 and 14-day observation.
NASA Astrophysics Data System (ADS)
Ghazali, Siti Nadia Aini; Mohamad, Zurina; Majid, Rohah A.; Appadu, Sivanesan
2017-07-01
This study presents the influence of ethylene glycol dimethacrylate (EGDMA) as a crosslinking agent through electron beam crosslinking process. Therefore, the effects of EGDMA on irradiated low density polyethylene/sepiolite (LDPE/SEP) nanocomposites on the tensile and thermal properties at 4 part per hundred resin (phr) sepiolite were investigated. The LDPE/SEP nanocomposites were prepared by melt mixing using twin screw extruder at 160 ˚C with a screw speed of 50 rpm. The nanocomposites were then undergone injection moulding process followed by irradiated using 2 MeV electron beam machine at doses ranging from 0 to 200 kGy in the air at ambient temperature. It was found that the tensile strength and Young's modulus were slightly increased with the presence of co-agent. The sample containing 4 phr sepiolite at 200 kGy showed 9% increase in tensile strength when EGDMA was added. However, the result of thermogravimetry analysis (TGA) showed some reduction in thermal stability of nanocomposites on 100 kGy irradiation dose. EGDMA had reduced the optimum irradiation dose without having any adverse effect on tensile and thermal properties.
Wang, Zhenwen; Zhao, Jun; Chen, Min; Yang, Minhao; Tang, Luyang; Dang, Zhi-Min; Chen, Fenghua; Huang, Miaoming; Dong, Xia
2014-11-26
In this work, electrically and thermally actuated triple shape memory polymers (SMPs) of chemically cross-linked polycyclooctene (PCO)-multiwalled carbon nanotube (MWCNT)/polyethylene (PE) nanocomposites with co-continuous structure and selective distribution of fillers in PCO phase are prepared. We systematically studied not only the microstructure including morphology and fillers' selective distribution in one phase of the PCO/PE blends, but also the macroscopic properties including thermal, mechanical, and electrical properties. The co-continuous window of the immiscible PCO/PE blends is found to be the volume fraction of PCO (vPCO) of ca. 40-70 vol %. The selective distribution of fillers in one phase of co-continuous blends is obtained by a masterbatch technique. The prepared triple SMP materials show pronounced triple shape memory effects (SMEs) on the dynamic mechanical thermal analysis (DMTA) and the visual observation by both thermal and electric actuations. Such polyolefin samples with well-defined microstructure, electrical actuation, and triple SMEs might have potential applications as, for example, multiple autochoke elements for engines, self-adjusting orthodontic wires, and ophthalmic devices.
Load Transmission Through Artificial Hip Joints due to Stress Wave Loading
NASA Astrophysics Data System (ADS)
Tanabe, Y.; Uchiyama, T.; Yamaoka, H.; Ohashi, H.
Since wear of the polyethylene (Ultra High Molecular Weight Polyethylene or UHMWPE) acetabular cup is considered to be the main cause of loosening of the artificial hip joint, the cross-linked UHMWPE with high durability to wear has been developed. This paper deals with impact load transmission through the complex of an artificial hip joint consisting of a UHMWPE acetabular cup (or liner), a metallic femoral head and stem. Impact compressive tests on the complex were performed using the split-Hopkinson pressure bar apparatus. To investigate the effects of material (conventional or cross-linked UHMWPE), size and setting angle of the liner, and test temperature on force transmission, the impact load transmission ratio (ILTR) was experimentally determined. The ILTR decreased with an increase of the setting angle independent of material and size of the liner, and test temperature. The ILTR values at 37°C were larger than those at 24 °C and 60°C. The ILTR also appeared to be affected by the type of material as well as size of the liner.
Ren, Yong; Wang, Guowei; Huang, Junlian
2007-06-01
A convenient approach is provided to prepare liquid-core nanocapsules by cross-linking an amphiphilic copolymer at an oil-water interface. The hydrophilic copolymer poly[(ethylene oxide)-co-glycidol] was prepared by anionic polymerization of ethylene oxide and ethoxyethyl glycidyl ether first, then the hydroxyl groups on the backbone were recovered after hydrolysis and partly modified by hydrophobic conjugated linoleic acid. The copolymer with multiple linoleate pendants was absorbed at an oil-water interface and then cross-linked to form stable nanocapsules. The mean diameter of the nanocapsule was below 350 nm, and the size distribution was relatively narrow (<0.2) at low concentrations of oil in acetone (<10 mg/mL). The particle size could be tuned easily by variation of the emulsification conditions. The nanocapsule was stable in water for at least 5 months, and the shell maintained its integrity after removal of the oily core by solvent. Pyrene was encapsulated in these nanocapsules, and a loading efficiency as high as 94% was measured by UV spectroscopy.
J-integral fracture toughness and tearing modulus measurement of radiation cross-linked UHMWPE.
Gomoll, A; Wanich, T; Bellare, A
2002-11-01
Radiation and chemical cross-linking of medical grade ultrahigh molecular weight polyethylene (UHMWPE) has recently been utilized in an effort to improve wear performance of total joint replacement components. However, reductions in mechanical properties with cross-linking are cause for concern regarding the use of cross-linked UHMWPE for high-stress applications such as in total knee replacement prostheses. In this study, the fracture behavior of radiation cross-linked UHMWPE was compared to that of uncross-linked UHMWPE. The Rice and Sorensen model that utilizes mechanical parameters obtained from uniaxial tensile and compact tension tests was used to calculate the steady state J-integral fracture toughness, Jss, for radiation cross-linked UHMWPE. Jss decreased monotonically with increase in radiation dose. UHMWPE exhibited tough, ductile tearing behavior with stable crack growth when it was cross-linked using a gamma radiation dose of 0-50 kGy. However, in cross-linked UHMWPE irradiated to a dose of 100 and 200 kGy, unstable fracture occurred spontaneously upon attaining the initial crack driving force, J1c. This indicates that a high degree of cross-linking is less desirable for high-stress applications in orthopaedic implants. However, a substantial increase in J1c, even at a low degree of cross-linking, suggests that a low degree of cross-linking may be beneficial for resistance to delamination and catastrophic failure, both of which require an initiation step for the fracture to propagate in the material. This mechanical test should, however, be considered along with fatigue tests and joint simulator testing before determination of an appropriate amount of cross-linking for total joint replacement prostheses that experience high stresses.
Cole, Adam J; David, Allan E; Wang, Jianxin; Galbán, Craig J; Hill, Hannah L; Yang, Victor C
2011-03-01
While successful magnetic tumor targeting of iron oxide nanoparticles has been achieved in a number of models, the rapid blood clearance of magnetically suitable particles by the reticuloendothelial system (RES) limits their availability for targeting. This work aimed to develop a long-circulating magnetic iron oxide nanoparticle (MNP) platform capable of sustained tumor exposure via the circulation and, thus, potentially enhanced magnetic tumor targeting. Aminated, cross-linked starch (DN) and aminosilane (A) coated MNPs were successfully modified with 5 kDa (A5, D5) or 20 kDa (A20, D20) polyethylene glycol (PEG) chains using simple N-Hydroxysuccinimide (NHS) chemistry and characterized. Identical PEG-weight analogues between platforms (A5 & D5, A20 & D20) were similar in size (140-190 nm) and relative PEG labeling (1.5% of surface amines - A5/D5, 0.4% - A20/D20), with all PEG-MNPs possessing magnetization properties suitable for magnetic targeting. Candidate PEG-MNPs were studied in RES simulations in vitro to predict long-circulating character. D5 and D20 performed best showing sustained size stability in cell culture medium at 37 °C and 7 (D20) to 10 (D5) fold less uptake in RAW264.7 macrophages when compared to previously targeted, unmodified starch MNPs (D). Observations in vitro were validated in vivo, with D5 (7.29 h) and D20 (11.75 h) showing much longer half-lives than D (0.12 h). Improved plasma stability enhanced tumor MNP exposure 100 (D5) to 150 (D20) fold as measured by plasma AUC(0-∞). Sustained tumor exposure over 24 h was visually confirmed in a 9L-glioma rat model (12 mg Fe/kg) using magnetic resonance imaging (MRI). Findings indicate that a polyethylene glycol modified, cross-linked starch-coated MNP is a promising platform for enhanced magnetic tumor targeting, warranting further study in tumor models. Copyright © 2010 Elsevier Ltd. All rights reserved.
Petis, Stephen M.; Vasarhelyi, Edward M.; Lanting, Brent A.; Howard, James L.; Naudie, Douglas D.R.; Somerville, Lyndsay E.; McCalden, Richard W.
2016-01-01
Background The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. Methods We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan–Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. Results A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0–10.6) years for cobalt-chrome and 7.8 (range 2.1–10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%–97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%–99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%–98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%–99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Conclusion Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up. PMID:26812409
Effects of sterilization on poly(ethylene glycol) hydrogels.
Kanjickal, Deenu; Lopina, Stephanie; Evancho-Chapman, M Michelle; Schmidt, Steven; Donovan, Duane
2008-12-01
The past few decades have witnessed a dramatic increase in the development of polymeric biomaterials. These biomaterials have to undergo a sterilization procedure before implantation. However, many sterilization procedures have been shown to profoundly affect polymer properties. Poly(ethylene glycol) hydrogels have gained increasing importance in the controlled delivery of therapeutics and in tissue engineering. We evaluated the effect of ethylene oxide (EtO), hydrogen peroxide (H(2)O(2)), and gamma sterilization of poly(ethylene glycol) hydrogels on properties relevant to controlled drug delivery and tissue engineering. We observed that the release of cyclosporine (CyA) (an immunosuppressive drug that is effective in combating tissue rejection following organ transplantation) was significantly affected by the type of sterilization. However, that was not the case with rhodamine B, a dye. Hence, the drug release characteristics were observed to be dependent not only on the sterilization procedure but also on the type of agent that needs to be delivered. In addition, differences in the swelling ratios for the sterilized and unsterilized hydrogels were statistically significant for 1:1 crosslinked hydrogels derived from the 8000 MW polymer. Significant differences were also observed for gamma sterilization for 1:1 crosslinked hydrogels derived from the 3350 MW polymer and also the 2:1 crosslinked hydrogels derived from the 8000 MW polymer. Atomic force microscopy (AFM) studies revealed that the roughness parameter for the unsterilized and EtO-sterilized PEG hydrogels remained similar. However, a statistically significant reduction of the roughness parameter was observed for the H(2)O(2) and gamma-sterilized samples. Electron spin resonance (ESR) studies on the unsterilized and the sterilized samples revealed the presence of the peroxy and the triphenyl methyl carbon radical in the samples. The gamma and the H(2)O(2)-sterilized samples were observed to have a much higher concentration of the radical pecies when compared with the EtO and the unsterilized samples. (c) 2008 Wiley Periodicals, Inc. J Biomed Mater Res, 2008.
A Solution-Doped Polymer Semiconductor:Insulator Blend for Thermoelectrics.
Kiefer, David; Yu, Liyang; Fransson, Erik; Gómez, Andrés; Primetzhofer, Daniel; Amassian, Aram; Campoy-Quiles, Mariano; Müller, Christian
2017-01-01
Poly(ethylene oxide) is demonstrated to be a suitable matrix polymer for the solution-doped conjugated polymer poly(3-hexylthiophene). The polarity of the insulator combined with carefully chosen processing conditions permits the fabrication of tens of micrometer-thick films that feature a fine distribution of the F4TCNQ dopant:semiconductor complex. Changes in electrical conductivity from 0.1 to 0.3 S cm -1 and Seebeck coefficient from 100 to 60 μV K -1 upon addition of the insulator correlate with an increase in doping efficiency from 20% to 40% for heavily doped ternary blends. An invariant bulk thermal conductivity of about 0.3 W m -1 K -1 gives rise to a thermoelectric Figure of merit ZT ∼ 10 -4 that remains unaltered for an insulator content of more than 60 wt%. Free-standing, mechanically robust tapes illustrate the versatility of the developed dopant:semiconductor:insulator ternary blends.
A Solution‐Doped Polymer Semiconductor:Insulator Blend for Thermoelectrics
Kiefer, David; Yu, Liyang; Fransson, Erik; Gómez, Andrés; Primetzhofer, Daniel; Amassian, Aram; Campoy‐Quiles, Mariano
2016-01-01
Poly(ethylene oxide) is demonstrated to be a suitable matrix polymer for the solution‐doped conjugated polymer poly(3‐hexylthiophene). The polarity of the insulator combined with carefully chosen processing conditions permits the fabrication of tens of micrometer‐thick films that feature a fine distribution of the F4TCNQ dopant:semiconductor complex. Changes in electrical conductivity from 0.1 to 0.3 S cm−1 and Seebeck coefficient from 100 to 60 μV K−1 upon addition of the insulator correlate with an increase in doping efficiency from 20% to 40% for heavily doped ternary blends. An invariant bulk thermal conductivity of about 0.3 W m−1 K−1 gives rise to a thermoelectric Figure of merit ZT ∼ 10−4 that remains unaltered for an insulator content of more than 60 wt%. Free‐standing, mechanically robust tapes illustrate the versatility of the developed dopant:semiconductor:insulator ternary blends. PMID:28105396
NASA Technical Reports Server (NTRS)
Nguyen, Baochau N.; Guo, Haiquan N.; McCorkle, Linda S.
2014-01-01
As aerospace applications become ever more demanding, novel insulation materials with lower thermal conductivity, lighter weight and higher use temperature are required to fit the aerospace application needs. Having nanopores and high porosity, aerogels are superior thermal insulators, among other things. The use of silica aerogels in general is quite restricted due to their inherent fragility, hygroscopic nature, and poor mechanical properties, especially in extereme aerospace environments. Our research goal is to develop aerogels with better mechanical and environmental stability for a variety of aeronautic and space applications including space suit insulation for planetary surface missions, insulation for inflatable structures for habitats, inflatable aerodynamic decelerators for entry, descent and landing (EDL) operations, and cryotank insulation for advance space propulsion systems. Different type of aerogels including organic-inorganic polymer reinforced (hybrid) silica-based aerogels, polyimide aerogels and inorganic aluminosilicate aerogels have been developed and examined.
NASA Technical Reports Server (NTRS)
Salyer, I. O.
1980-01-01
The electron irradiation conditions required to prepare thermally from stable high density polyethylene (HDPE) were defined. The conditions were defined by evaluating the heat of fusion and the melting temperature of several HDPE specimens. The performance tests conducted on the specimens, including the thermal cycling tests in the thermal energy storage unit are described. The electron beam irradiation tests performed on the specimens, in which the total radiation dose received by the pellets, the electron beam current, the accelerating potential, and the atmospheres were varied, are discussed.
Kempe, Michael D.; Miller, David C.; Wohlgemuth, John H.; ...
2016-01-08
As creep of polymeric materials is potentially a safety concern for photovoltaic modules, the potential for module creep has become a significant topic of discussion in the development of IEC 61730 and IEC 61215. To investigate the possibility of creep, modules were constructed, using several thermoplastic encapsulant materials, into thin-film mock modules and deployed in Mesa, Arizona. The materials examined included poly(ethylene)-co-vinyl acetate (EVA, including formulations both cross-linked and with no curing agent), polyethylene/polyoctene copolymer (PO), poly(dimethylsiloxane) (PDMS), polyvinyl butyral (PVB), and thermoplastic polyurethane (TPU). The absence of creep in this experiment is attributable to several factors of which themore » most notable one was the unexpected cross-linking of an EVA formulation without a cross-linking agent. It was also found that some materials experienced both chain scission and cross-linking reactions, sometimes with a significant dependence on location within a module. The TPU and EVA samples were found to degrade with cross-linking reactions dominating over chain scission. In contrast, the PO materials degraded with chain scission dominating over cross-linking reactions. Furthermore, we found no significant indications that viscous creep is likely to occur in fielded modules capable of passing the qualification tests, we note that one should consider how a polymer degrades, chain scission or cross-linking, in assessing the suitability of a thermoplastic polymer in terrestrial photovoltaic applications.« less
3D cell entrapment in crosslinked thiolated gelatin-poly(ethylene glycol) diacrylate hydrogels
Fu, Yao; Xu, Kedi; Zheng, Xiaoxiang; Giacomin, A. Jeffrey; Mix, Adam W.; Kao, Weiyuan John
2012-01-01
The combined use of natural ECM components and synthetic materials offers an attractive alternative to fabricate hydrogel-based tissue engineering scaffolds to study cell-matrix interactions in three-dimensions (3D). A facile method was developed to modify gelatin with cysteine via a bifunctional PEG linker, thus introducing free thiol groups to gelatin chains. A covalently crosslinked gelatin hydrogel was fabricated using thiolated gelatin and poly(ethylene glycol) diacrylate (PEGdA) via thiol-ene reaction. Unmodified gelatin was physically incorporated in a PEGdA-only matrix for comparison. We sought to understand the effect of crosslinking modality on hydrogel physicochemical properties and the impact on 3D cell entrapment. Compared to physically incorporated gelatin hydrogels, covalently crosslinked gelatin hydrogels displayed higher maximum weight swelling ratio (Qmax), higher water content, significantly lower cumulative gelatin dissolution up to 7 days, and lower gel stiffness. Furthermore, fibroblasts encapsulated within covalently crosslinked gelatin hydrogels showed extensive cytoplasmic spreading and the formation of cellular networks over 28 days. In contrast, fibroblasts encapsulated in the physically incorporated gelatin hydrogels remained spheroidal. Hence, crosslinking ECM protein with synthetic matrix creates a stable scaffold with tunable mechanical properties and with long-term cell anchorage points, thus supporting cell attachment and growth in the 3D environment. PMID:21955690
Welsch, Nicole; Lyon, L Andrew
2017-01-01
We present a systematic study of self-cross-linked microgels formed by precipitation polymerization of oligo ethylene glycol methacrylates. The cross-linking density of these microgels and, thus, the network flexibility can be easily tuned through the modulation of the reaction temperature during polymerization. Microgels prepared in absence of any difunctional monomer, i.e. cross-linker, show enhanced deformability and particle spreading on solid surfaces as compared to microgels cross-linked with varying amounts of poly(ethylene glycol diacrylate) (PEG-DA) in addition to self-crosslinking. Particles prepared at low reaction temperatures exhibit the highest degree of spreading due to the lightly cross-linked and flexible polymer network. Moreover, AFM force spectroscopy studies suggest that cross-linker-free microgels constitute of a more homogeneous polymer network than PEG-DA cross-linked particles and have elastic moduli at the particle apex that are ~5 times smaller than the moduli of 5 mol-% PEG-DA cross-linked microgels. Resistive pulse sensing experiments demonstrate that microgels prepared at 75 and 80°C without PEG-DA are able to deform significantly to pass through nanopores that are smaller than the microgel size. Additionally, we found that polymer network flexibility of microgels is a useful tool to control the formation of particle dewetting patterns. This offers a promising new avenue for build-up of 2D self-assembled particle structures with patterned chemical and mechanical properties.
Lyon, L. Andrew
2017-01-01
We present a systematic study of self-cross-linked microgels formed by precipitation polymerization of oligo ethylene glycol methacrylates. The cross-linking density of these microgels and, thus, the network flexibility can be easily tuned through the modulation of the reaction temperature during polymerization. Microgels prepared in absence of any difunctional monomer, i.e. cross-linker, show enhanced deformability and particle spreading on solid surfaces as compared to microgels cross-linked with varying amounts of poly(ethylene glycol diacrylate) (PEG-DA) in addition to self-crosslinking. Particles prepared at low reaction temperatures exhibit the highest degree of spreading due to the lightly cross-linked and flexible polymer network. Moreover, AFM force spectroscopy studies suggest that cross-linker-free microgels constitute of a more homogeneous polymer network than PEG-DA cross-linked particles and have elastic moduli at the particle apex that are ~5 times smaller than the moduli of 5 mol-% PEG-DA cross-linked microgels. Resistive pulse sensing experiments demonstrate that microgels prepared at 75 and 80°C without PEG-DA are able to deform significantly to pass through nanopores that are smaller than the microgel size. Additionally, we found that polymer network flexibility of microgels is a useful tool to control the formation of particle dewetting patterns. This offers a promising new avenue for build-up of 2D self-assembled particle structures with patterned chemical and mechanical properties. PMID:28719648
Development and analysis of insulation constructions for aerospace wiring applications
NASA Astrophysics Data System (ADS)
Slenski, George A.; Woodford, Lynn M.
1993-03-01
The Wright Laboratory Materials Directorate at WPAFB, Ohio recently completed a research and development program under contract with the McDonnell Douglas Aerospace Company, St. Louis, Missouri. Program objectives were to develop wire insulation performance requirements, evaluate candidate insulations, and prepare preliminary specification sheets on the most promising candidates. Aircraft wiring continues to be a high maintenance item and a major contributor to electrically-related aircraft mishaps. Mishap data on aircraft show that chafing of insulation is the most common mode of wire failure. Improved wiring constructions are expected to increase aircraft performance and decrease costs by reducing maintenance actions. In the laboratory program, new insulation constructions were identified that had overall improved performance in evaluation tests when compared to currently available MIL-W-81381 and MIL-W-22759 wiring. These insulations are principally aromatic polyimide and crosslinked ethylene tetrafluoroethylene (ETFE), respectively. Candidate insulations identified in preliminary specification sheets were principally fluoropolymers with a polyimide inner layer. Examples of insulation properties evaluated included flammability, high temperature mechanical and electrical performance, fluid immersion, and susceptibility to arc propagation under applied power chafing conditions. Potential next generation wire insulation materials are also reviewed.
Studies on water treeing and chemiluminescence on irradiated polyethylene
DOE Office of Scientific and Technical Information (OSTI.GOV)
Notingher, P.V.; Ciuprina, F.; Radu, I.
The effect of {gamma}-radiations on the growth kinetics of water trees is examined using the CNRS laboratory model in LDPE samples of different origins. The effect of radiations on the material is studied from crosslinking degree measurements, IRTF spectroscopy and chemiluminescence. Correlations between the non-uniformity of the degradation and the growth of water trees are observed.
Kubo, Takuya; Furuta, Hayato; Naito, Toyohiro; Sano, Tomoharu; Otsuka, Koji
2017-06-29
Selective adsorption of carbohydrates and glycoproteins was effectively achieved by molecularly imprinted hydrogels (MIHs) with a poly(ethylene glycol) (PEG)-based crosslinker and 4-vinylphenylboronic acid. In addition, an MIH with a novel boronic acid monomer provided selective adsorption and enabled visible detection of fructose.
Foam vessel for cryogenic fluid storage
Spear, Jonathan D [San Francisco, CA
2011-07-05
Cryogenic storage and separator vessels made of polyolefin foams are disclosed, as are methods of storing and separating cryogenic fluids and fluid mixtures using these vessels. In one embodiment, the polyolefin foams may be cross-linked, closed-cell polyethylene foams with a density of from about 2 pounds per cubic foot to a density of about 4 pounds per cubic foot.
Chowdhury, Sanjib Chandra; Okabe, Tomonaga; Nishikawa, Masaaki
2010-02-01
We investigate the effects of the vacancy defects (i.e., missing atoms) in carbon nanotubes (CNTs) on the interfacial shear strength (ISS) of the CNT-polyethylene composite with the molecular dynamics simulation. In the simulation, the crystalline polyethylene matrix is set up in a hexagonal array with the polymer chains parallel to the CNT axis. Vacancy defects in the CNT are introduced by removing the corresponding atoms from the pristine CNT (i.e., CNT without any defect). Three patterns of vacancy defects with three different sizes are considered. Two types of interfaces, with and without cross-links between the CNT and the matrix are also considered here. Polyethylene chains are used as cross-links between the CNT and the matrix. The Brenner potential is used for the carbon-carbon interaction in the CNT, while the polymer is modeled by a united-atom potential. The nonbonded van der Waals interaction between the CNT and the polymer matrix and within the polymer matrix itself is modeled with the Lennard-Jones potential. To determine the ISS, we conduct the CNT pull-out from the polymer matrix and the ISS has been estimated with the change of total potential energy of the CNT-polymer system. The simulation results reveal that the vacancy defects significantly influence the ISS. Moreover, the simulation clarifies that CNT breakage occurs during the pull-out process for large size vacancy defect which ultimately reduces the reinforcement.
Malatray, Matthieu; Roux, Jean-Paul; Gunst, Stanislas; Pibarot, Vincent; Wegrzyn, Julien
2017-03-01
Dual mobility cup (DMC) consists of a cobalt-chromium (CoCr) alloy cup articulated with a polyethylene (PE) mobile component capturing the femoral head in force using a snap-fit technique. This biomechanical study was the first to evaluate and compare the generation of cracks in the retentive area of DMC mobile components made of highly crosslinked PE (XLPE) or conventional ultra-high molecular weight PE (UHMWPE). Eighty mobile components designed for a 52-mm diameter Symbol® DMC (Dedienne Santé, Mauguio, France) and a 28-mm diameter femoral head were analyzed. Four groups of 20 mobile components were constituted according to the PE material: raw UHMWPE, sterilized UHMWPE, annealed XLPE and remelted XLPE. Ten mobile components in each group were impacted with a 28-mm diameter CoCr femoral head using a snap-fit technique. The occurrence, location and area of the cracks in the retentive area were investigated using micro-CT (Skyscan 1176®, Bruker, Aarsellar, Belgium) with a 35 μm nominal isotropic voxel size by two observers blinded to the PE material and impaction or not of the mobile components. Compared to conventional UHMWPE, the femoral head snap-fit did not generate more or wider cracks in the retentive area of annealed or remelted XLPE mobile components. This biomechanical study suggests that XLPE in DMC could be a safe alternative to conventional UHMWPE regarding the generation of cracks in the retentive area related to the femoral head snap-fit.
NASA Astrophysics Data System (ADS)
Nho, Young-Chang; Sohn, Joon-Yong; Shin, Junhwa; Park, Jong-Seok; Lim, Yoon-Mook; Kang, Phil-Hyun
2017-03-01
Although micro-porous membranes made of polyethylene (PE) offer excellent mechanical strength and chemical stability, they exhibit large thermal shrinkage at high temperature, which causes a short circuit between positive and negative electrodes in cases of unusual heat generation. We tried to develop a new technology to reduce the thermal shrinkage of PE separators by introducing γ-Al2O3 particles treated with coupling agent on PE separators. Nanocomposite γ-Al2O3/PE separators were prepared by the dip coating of polyethylene(PE) separators in γ-Al2O3/poly(vinylidenefluoride-hexafluoropropylene) (PVDF-HFP)/crosslinker (1,3,5-trially-1,3,5-triazine-2,4,6(1 H,3 H,5 H)-trione (TTT) solution with humidity control followed by electron beam irradiation. γ-Al2O3/PVDF-HFP/TTT (95/5/2)-coated PE separator showed the highest electrolyte uptake (157%) and ionic conductivity (1.3 mS/cm). On the basis of the thermal shrinkage test, the nanocomposite γ-Al2O3/PE separators containing TTT irradiated by electron beam exhibited a higher thermal resistance. Moreover, a linear sweep voltammetry test showed that the irradiated nanocomposite γ-Al2O3/PE separators have electrochemical stabilities of up to 5.0 V. In a battery performance test, the coin cell assembled with γ-Al2O3/PVDF-HFP/TTT-coated PE separator showed excellent discharge cycle performance.
High-explosive driven crowbar switch
Dike, Robert S.; Kewish, Jr., Ralph W.
1976-01-13
The disclosure relates to a compact explosive driven switch for use as a low resistance, low inductance crowbar switch. A high-explosive charge extrudes a deformable conductive metallic plate through a polyethylene insulating layer to achieve a hard current contact with a supportive annular conductor.
Risk factors for total hip arthroplasty aseptic revision.
Khatod, Monti; Cafri, Guy; Namba, Robert S; Inacio, Maria C S; Paxton, Elizabeth W
2014-07-01
The purpose of this study was to evaluate patient, operative, implant, surgeon, and hospital factors associated with aseptic revision after primary THA in patients registered in a large US Total Joint Replacement Registry. A total of 35,960 THAs registered from 4/2001-12/2010 were evaluated. The 8-year survival rate was 96.7% (95% CI 96.4%-97.0%). Females had a higher risk of aseptic revision than males. Hispanic and Asian patients had a lower risk of revision than white patients. Ceramic-on-ceramic, ceramic-on-conventional polyethylene, and metal-on-conventional polyethylene bearing surfaces had a higher risk of revision than metal-on-highly cross-linked polyethylene. Body mass index, health status, diabetes, diagnosis, fixation, approach, bilateral procedures, head size, surgeon fellowship training, surgeon and hospital volume were not revision risk factors. Copyright © 2014 Elsevier Inc. All rights reserved.
Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics
Grindy, Scott C.; Learsch, Robert; Mozhdehi, Davoud; Cheng, Jing; Barrett, Devin G.; Guan, Zhibin; Messersmith, Phillip B.; Holten-Andersen, Niels
2015-01-01
In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or copolymer-block design1. Here, by means of a model system of 4-arm poly(ethylene glycol) hydrogels crosslinked with multiple, kinetically distinct dynamic metal-ligand coordinate complexes, we show that polymer materials with decoupled spatial structure and mechanical performance can be designed. By tuning the relative concentration of two types of metal-ligand crosslinks, we demonstrate control over the material’s mechanical hierarchy of energy-dissipating modes under dynamic mechanical loading, and therefore the ability to engineer a priori the viscoelastic properties of these materials by controlling the types of crosslinks rather than by modifying the polymer itself. This strategy to decouple material mechanics from structure may inform the design of soft materials for use in complex mechanical environments. PMID:26322715
NASA Astrophysics Data System (ADS)
Sangkota, V. D. A.; Lusiana, R. A.; Astuti, Y.
2018-04-01
Crosslinking and grafting reactions are required to modify the functional groups on chitosan to increase the number of its active groups. In this study, crosslinking reaction of succinic acid and grafting reaction of heparin on chitosan were conducted to produce a membrane as a candidate of a hemodialysis membrane. The mole ratio between chitosan and succinate acids was varied to obtain the best composition of modified materials. By blending all the material composition with PVA-PEG, the blend was transformed into a membrane. The resulted membrane was then characterized by various test methods such as tests of thickness, weight, water uptake, pH resistance, tensile strength and membrane hydrophilicity. The results showed that the best composition of the membrane reached in the addition of 0.011 gram of succinic acid proved by its highest mechanical strength compared to the other membranes.
Liang, Yingkai; Kiick, Kristi L
2016-02-08
Novel, liposome-cross-linked hybrid hydrogels cross-linked by the Michael-type addition of thiols with maleimides were prepared via the use of maleimide-functionalized liposome cross-linkers and thiolated polyethylene glycol (PEG) polymers. Gelation of the materials was confirmed by oscillatory rheology experiments. These hybrid hydrogels are rendered degradable upon exposure to thiol-containing molecules such as glutathione (GSH), via the incorporation of selected thioether succinimide cross-links between the PEG polymers and liposome nanoparticles. Dynamic light scattering (DLS) characterization confirmed that intact liposomes were released upon network degradation. Owing to the hierarchical structure of the network, multiple cargo molecules relevant for chemotherapies, namely doxorubicin (DOX) and cytochrome c, were encapsulated and simultaneously released from the hybrid hydrogels, with differential release profiles that were driven by degradation-mediated release and Fickian diffusion, respectively. This work introduces a facile approach for the development of advanced, hybrid drug delivery vehicles that exhibit novel chemical degradation.
Zhang, Xuan; Wang, Youpeng; Li, Guo; Liu, Zhaotie; Liu, Zhongwen; Jiang, Jinqiang
2017-01-01
An amphiphilic block copolymer of poly(ethylene oxide)-b-poly((N-methacryloxy phthalimide)-co-(7-(4-vinyl-benzyloxyl)-4-methylcoumarin)) (PEO 45 -b-P(MAPI 36 -co-VBC 4 )) is designed to improve the micellar stability during the photo-triggered release of hydrophobic cargoes. Analysis of absorption and emission spectra, solution transmittance, dynamic light scattering, and transmission electron microscopy supports that polymer micelles of PEO 45 -b-P(MAPI 36 -co-VBC 4 ) upon the combinational irradiation of 365 and 254 nm light can be solubilized through the photolysis of phthalimide esters and simultaneously crosslinked via the partially reversible photo-dimerization of coumarins. The photo-triggered release experiment shows that the leakage of doxorubicin molecules from crosslinked micelles can be predictably regulated by controlling the irradiation time of 365 and 254 nm light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
New Materials for the Repair of Polyimide Electrical Wire Insulation
NASA Technical Reports Server (NTRS)
2008-01-01
Two viable polyimide backbone materials have been identified that will allow the repair of polyimide electrical wire insulation found on the Space Shuttle and other aging aircraft. This identification is the outcome of ongoing efforts to assess the viability of using such polyimides and polyimide precursors (polyamic acids [PAAs]) as repair materials for aging polyimide electrical wire insulation. These repair materials were selected because they match the chemical makeup of the underlying wire insulation as closely as possible. This similarity allows for maximum compatibility, coupled with the outstanding physical properties of polyimides. The two polyimide backbone materials allow the polymer to be extremely flexible and to melt at low temperatures. A polymer chain end capping group that allows the polymer to crosslink into a nonflowable repair upon curing at around 200 C was also identified.
NASA Technical Reports Server (NTRS)
Fujita, O.; Nishizawa, K.; Ito, K.; Olson, S. L.; Kashigawa, T.
2001-01-01
The effect of slow external flow on solid combustion is very important from the view of fire safety in space because the solid material in spacecraft is generally exposed to the low air flow for ventilation. Further, the effect of low external flow on fuel combustion is generally fundamental information for industrial combustion system, such as gas turbine, boiler incinerator and so on. However, it is difficult to study the effect of low external flow on solid combustion in normal gravity, because the buoyancy-induced flow strongly disturbs the flow field, especially for low flow velocity. In this research therefore, the effect of slow external flow on opposed flame spreading over polyethylene (PE) wire insulation have been investigated in microgravity. The microgravity environment was provided by Japan Microgravity Center (JAMIC) in Japan and KC-135 at NASA GRC. The tested flow velocity range is 0-30cm/s with different oxygen concentration and inert gas component.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Alfred-Duplan, C.; Musso, J.; Gavarri, J.R.
1994-05-01
Composite pellets were prepared from low-density polyethylene (LDPE) and vanadium dioxide powders. The VO[sub 2] pigments are used for their insulating-to-metallic transition at 341 K in order to obtain electrically variable composite materials. The volume fractions of VO[sub 2] powders vary from [phi] = 0 to [phi] = 0.55. The composite samples are characterized by X-ray diffraction and scanning electron microscopy. Complex impedance analysis in the frequency range 10[sup [minus]1] to 10[sup 6]. Hz is carried out at room temperature and at T = 363 K, to observe the insulator-metal transition of VO[sub 2] pigments dispersed in the polymer host.more » The variation of the complex impedance modulus [vert bar]Z[vert bar] with frequency and with VO[sub 2] volume fraction ([phi]) is discussed. A specific (R, C) impedance model permits interpretation of the experimental results in terms of percolation; the observed variations can be accounted for.« less
NASA Astrophysics Data System (ADS)
Mebarki, Fouzia
The aim of this study is to examine the possibility of using thermoplastic composite materials for electrical applications such as supports of automotive engine ignition systems. We are particularly interested in composites based on recycled polyethylene terephtalate (PET). Conventional isolations like PET cannot meet the new prescriptive requirements. The introduction of reinforcement materials, such as glass fibers and mica can improve the mechanical characteristics of these materials. However, this enhancement may also reduce electrical properties especially since these composites have to be used under severe thermal and electric stresses. In order to estimate PET composite insulation lifetimes, accelerated aging tests were carried out at temperatures ranging from room temperature to 140°C and at a frequency of 300Hz. Studies at high temperature will help to identify the service temperature of candidate materials. Dielectric breakdown tests have been made on a large number of samples according to the standard of dielectric strength tests of solid insulating ASTM D-149. These tests have to identify the problematic samples and to check solid insulation quality. The different knowledge gained from this analysis was used to predict material performance. This will give the company the possibility to improve existing formulations and subsequently develop a material having electrical and thermal properties suitable for this application.
Ghanian, Mohammad Hossein; Mirzadeh, Hamid; Baharvand, Hossein
2018-05-14
A dual cross-linking strategy was developed to answer the urgent need for fatigue-resistant, cytocompatible, and in situ forming tough hydrogels. Clickable, yet calcium-binding derivatives of alginate were synthesized by partial substitution of its carboxyl functionalities with furan, which could come into Diels-Alder click reaction with maleimide end groups of a four arm poly(ethylene glycol) cross-linker. Tuning the cooperative viscoelastic action of transient ionic and permanent click cross-links within the single network of alginate provided a soft tough hydrogel with a set of interesting features: (i) immediate self-recovery under cyclic loading, (ii) highly efficient and autonomous self-healing upon fracture, (iii) in situ forming ability for molding and minimally invasive injection, (iv) capability for viable cell encapsulation, and (v) reactivity for on-demand biomolecule conjugation. The facile strategy is applicable to a wide range of natural and synthetic polymers by introducing the calcium binding and click reacting functional groups and can broaden the use of tough hydrogels in load-bearing, cell-laden applications such as soft tissue engineering and bioactuators.
Miao, Tianxin; Fenn, Spencer L.; Charron, Patrick N.; Oldinski, Rachael A.
2015-01-01
β-cyclodextrin (β-CD), with a lipophilic inner cavity and hydrophilic outer surface, interacts with a large variety of non-polar guest molecules to form non-covalent inclusion complexes. Conjugation of β-CD onto biomacromolecules can form physically-crosslinked hydrogel networks upon mixing with a guest molecule. Herein describes the development and characterization of self-healing, thermo-responsive hydrogels, based on host-guest inclusion complexes between alginate-graft-β-CD and Pluronic® F108 (poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)). The mechanics, flow characteristics, and thermal response were contingent on the polymer concentrations, and the host-guest molar ratio. Transient and reversible physical crosslinking between host and guest polymers governed self-assembly, allowing flow under shear stress, and facilitating complete recovery of the material properties within a few seconds of unloading. The mechanical properties of the dual-crosslinked, multi-stimuli responsive hydrogels were tuned as high as 30 kPa at body temperature, and are advantageous for biomedical applications such as drug delivery and cell transplantation. PMID:26509214
Jing, Zi-Wei; Ma, Zhi-Wei; Li, Chen; Jia, Yi-Yang; Luo, Min; Ma, Xi-Xi; Zhou, Si-Yuan; Zhang, Bang-Le
2017-02-15
The covalently cross-linked chitosan-poly(ethylene glycol) 1540 derivatives have been developed as a controlled release system with potential for the delivery of protein drug. The swelling characteristics of the hydrogels based on these derivatives as the function of different PEG content and the release profiles of a model protein (bovine serum albumin, BSA) from the hydrogels were evaluated in simulated gastric fluid with or without enzyme in order to simulate the gastrointestinal tract conditions. The derivatives cross-linked with difunctional PEG 1540 -dialdehyde via reductive amination can swell in alkaline pH and remain insoluble in acidic medium. The cumulative release amount of BSA was relatively low in the initial 2h and increased significantly at pH 7.4 with intestinal lysozyme for additional 12h. The results proved that the release-and-hold behavior of the cross-linked CS-PEG 1540 H-CS hydrogel provided a swell and intestinal enzyme controlled release carrier system, which is suitable for oral protein drug delivery. Copyright © 2016 Elsevier Ltd. All rights reserved.
The impact of electron beam irradiation on Low density polyethylene and Ethylene vinyl acetate
NASA Astrophysics Data System (ADS)
Sabet, Maziyar; Soleimani, Hassan
2017-05-01
Improvement of measured gel content, hardness, tensile strength and elongation at break of Ethylene vinyl acetate (EVA) have confirmed positive effect of electron beam irradiation on EVA. Results obtained from both gel content tests show that degree of cross-linking in amorphous regions is dependent on dose. A significant improvement in tensile strength of neat EVA samples is obtained upon electron-beam radiation up to 210 kGy. Similarly, hardness properties of Low-density polyethylene (LDPE) improvewith increasing electron beam irradiation. This article deals with the impacts of electron beam (EB) irradiation on the properties of LDPE and Ethylene-Vinyl Acetate (EVA) as the two common based formulations for wire and cable applications.
Shear and elongational rheology of photo-oxidative degraded HDPE and LLDPE
NASA Astrophysics Data System (ADS)
Wagner, Manfred Hermann; Zheng, Wang; Wang, Peng; Talamante, Sebastián Ramos; Narimissa, Esmaeil
2017-05-01
The effect of photo-oxidative degradation of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) was investigated by linear and non-linear rheological measurements. The linear-viscoelastic rheological measurements were performed at different temperatures, while the elongational viscosity was measured at 170°C and at different strain rates. The rheological data are indicative of structural changes caused by photo-oxidative degradation including formation of long-chain branches (LCB), cross-linking, and chain scission, and they revealed a cyclic and continuing competition between chain scission and LCB/gel formation. These findings are supported by additional FTIR measurements and direct measurements of the gel content of the degraded samples.
Effect of [gamma]-irradiation on latent tracks of polyethylene terephthalate (PET) film
NASA Astrophysics Data System (ADS)
Hiroki, A.; Asano, M.; Yamaki, T.; Yoshida, M.
2005-04-01
The pre-treatment effect of γ-irradiation on latent tracks of polyethylene terephthalate (PET) films bombarded with swift heavy ions was investigated by electric conductometry and scanning electron microscope (SEM) observation. The Xe-ion bombarded PET films were etched for 6 h in 0.2 M NaOH aqueous solution at 70 °C to prepare track-etched membranes. As γ-irradiation doses increased in the range of 0-160 kGy, the surface pore diameter obtained by SEM observation decreased while that obtained by conductometry became large. This inconsistent result between the two methods was due to an increase in the crosslinked region in the latent tracks caused by γ-irradiation.
Antimicrobial Wound Dressing. Phase 1
1987-06-11
12 a. Antimicrobial Sensitivity Tests 12 b. Anin.il Model 13 5. Preparatiua of Microcapsules 14 B. Results 15 1. AIn Vit Diffusion 15 a. PVA... Microcapsules 35 Table 5 Tetracycline Hydrochloride Cellulose 36 Triacetate Microcapsules Table 6 Polyethylene Oxide Hydrogels 37 Table 7 Swelling of...Water and Crosslinking Effect Figure 24 In Vi trq Chlorhexidine Release 70 Polyacrylamide Hydrogel - Microcapsules Figure 25 In _Vitro Tetracycline
Kubo, Takuya; Nishimura, Naoki; Furuta, Hayato; Kubota, Kei; Naito, Toyohiro; Otsuka, Koji
2017-11-10
We report novel capillary gel electrophoresis (CGE) with poly(ethylene glycol) (PEG)-based hydrogels for the effective separations of biomolecules containing sugars and DNAs based on a molecular size effect. The gel capillaries were prepared in a fused silica capillary modified with 3-(trimethoxysilyl)propylmethacrylate using a variety of the PEG-based hydrogels. After the fundamental evaluations in CGE regarding the separation based on the molecular size effect depending on the crosslinking density, the optimized capillary provided the efficient separation of glucose ladder (G1 to G20). In addition, another capillary showed the successful separation of DNA ladder in the range of 10-1100 base pair, which is superior to an authentic acrylamide-based gel capillary. For both glucose and DNA ladders, the separation ranges against the molecular size were simply controllable by alteration of the concentration and/or units of ethylene oxide in the PEG-based crosslinker. Finally, we demonstrated the separations of real samples, which included sugars carved out from monoclonal antibodies, mAbs, and then the efficient separations based on the molecular size effect were achieved. Copyright © 2017 Elsevier B.V. All rights reserved.
In situ formation of leak-free polyethylene glycol (PEG) membranes in microfluidic fuel cells.
Ho, W F; Lim, K M; Yang, K-L
2016-11-29
Membraneless microfluidic fuel cells operated under two co-laminar flows often face serious fuel cross-over problems, especially when flow rates are close to zero. In this study, we show that polyethylene glycol (PEG) monomers can be cross-linked inside microfluidic channels to form leak-free PEG membranes, which prevent mixing of two incompatible electrolyte solutions while allowing diffusion of certain molecules (e.g. glucose) and ions. By using PEG monomers of different molecular weights and cross-linking conditions, we are able to tailor selectivity of the membrane to allow passage of glucose while blocking larger molecules such as trypan blue. As a proof of principle, a microfluidic fuel cell with a PEG membrane and two incompatible electrolytes (acid and base) is demonstrated. Thanks to the leak-free nature of the PEG membrane, these two electrolytes do not mix together even at very slow flow rates. This microfluidic fuel cell is able to generate a voltage up to ∼450 mV from 10 mM of glucose with a flow rate of 20 μL min -1 . This microfluidic fuel cell is potentially useful as a miniature power source for many applications.
Improved self-healing of polyethylene/carbon black nanocomposites by their shape memory effect.
Wang, Xiaoyan; Zhao, Jun; Chen, Min; Ma, Lan; Zhao, Xiaodong; Dang, Zhi-Min; Wang, Zhenwen
2013-02-07
In this work, the improved self-healing of cross-linked polyethylene (PE) (cPE)/carbon black (CB) nanocomposites by their shape memory effect (SME) is investigated. CB nanoparticles are found to be homogeneously dispersed in the PE matrix and significantly increase the strength of the materials. Compared with the breaking of linear PE (lPE) at the melting temperature (T(m)), the cPE and cPE/CB nanocomposites still have high strength above T(m) due to the formation of networks. The cPE and cPE/CB nanocomposites show both high strain fixity ratio (R(f)) and high strain recovery ratio (R(r)). Crystallization-induced elongation is observed for all the prepared shape memory polymer (SMP) materials and the effect becomes less remarkable with increasing volume fraction of CB nanoparticles (v(CB)). The scratch self-healing tests show that the cross-linking of PE matrix, the addition of CB nanoparticles, and the previous stretching in the direction perpendicular to the scratch favor the closure of the scratch and its complete healing. This SME-aided self-healing could have potential applications in diverse fields such as coating and structure materials.
Kang, Lu; Galvin, Alison L.; Brown, Thomas D.; Jin, Zhongmin; Fisher, John
2008-01-01
A computational model has been developed to quantify the degree of cross-shear of a polyethylene pin articulating against a metallic plate, based on the direct simulation of a multidirectional pin-on-plate wear machine. The principal molecular orientation (PMO) was determined for each polymer site. The frictional work in the direction perpendicular to the PMO was assumed to produce the greatest orientation softening (Wang et al., 1997). The cross-shear ratio (CS) was defined as the frictional work perpendicular to the PMO direction, divided by the total frictional work. Cross-shear on the pin contact surface was location-specific, and of continuously changing magnitude because the direction of frictional force continuously changed due to pin rotation. The polymer pin motion was varied from a purely linear track (CS=0) up to a maximum rotation of ±55° (CS=0.254). The relationship between wear factors (K) measured experimentally and theoretically predicted CS was defined using logarithmic functions for both conventional and highly cross-linked UHMWPE. Cross-shear increased the apparent wear factor for both polyethylenes by more than 5-fold compared to unidirectional wear. PMID:17936763
Polyimide Aerogels Using Triisocyanate as Cross-linker.
Nguyen, Baochau N; Meador, Mary Ann B; Scheiman, Daniel; McCorkle, Linda
2017-08-16
A family of polyimide (PI)-based aerogels is produced using Desmodur N3300A, an inexpensive triisocyanate, as the cross-linker. The aerogels are prepared by cross-linking amine end-capped polyimide oligomers with the triisocyanate. The polyimide oligomers are formulated using 2,2'-dimethylbenzidine, 4,4'-oxydianiline, or mixtures of both diamines, combined with 3,3',4,4'-biphenyltetracarboxylic dianhydride, and are chemically imidized at room temperature. Depending on the backbone chemistry, chain length, and polymer concentration, density of the aerogels ranged from 0.06 to 0.14 g/cm 3 and Brunauer-Emmett-Teller surface areas ranged from 350 to 600 m 2 /g. Compressive moduli of these aerogels were as high as 225 MPa, which are comparable to, or higher than, those previously reported prepared with similar backbone structures but with other cross-linkers. Because of their lower cost and commercial availability as cross-linker, the aerogels may have further potential as insulation for building and construction, clothing, sporting goods, and automotive applications, although lower-temperature stability may limit their use in some aerospace applications.
Dependence of nanomechanical modification of polymers on plasma-induced cross-linking
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tajima, S.; Komvopoulos, K.
2007-01-01
The nanomechanical properties of low-density polyethylene (LDPE) modified by inductively coupled, radio-frequency Ar plasma were investigated by surface force microscopy. The polymer surface was modified under plasma conditions of different ion energy fluences and radiation intensities obtained by varying the sample distance from the plasma power source. Nanoindentation results of the surface stiffness versus maximum penetration depth did not reveal discernible differences between untreated and plasma-treated LDPE, presumably due to the small thickness of the modified surface layer that resulted in a substrate effect. On the contrary, nanoscratching experiments demonstrated a significant increase in the surface shear resistance of plasma-modifiedmore » LDPE due to chain cross-linking. These experiments revealed an enhancement of cross-linking with increasing ion energy fluence and radiation intensity, and a tip size effect on the friction force and dominant friction mechanisms (adhesion, plowing, and microcutting). In addition, LDPE samples with a LiF crystal shield were exposed to identical plasma conditions to determine the role of vacuum ultraviolet (VUV) and ultraviolet (UV) radiation in the cross-linking process. The cross-linked layer of plasma-treated LDPE exhibited much higher shear strength than that of VUV/UV-treated LDPE. Plasma-induced surface modification of the nanomechanical properties of LDPE is interpreted in the context of molecular models of the untreated and cross-linked polymer surfaces derived from experimental findings.« less
Wu, Yukun; Lai, Quanyong; Lai, Shuqi; Wu, Jing; Wang, Wei; Yuan, Zhi
2014-06-01
Polymeric micelles formed in aqueous solution by assembly of amphiphilic block copolymers have been extensively investigated due to their great potential as drug carriers. However, the stability of polymeric assembly is still one of the major challenges in delivering drugs to tissues and cells. Here, we report a facile route to fabricate core cross-linked (CCL) micelles using an enzymatic polymerization as the cross-linking method. We present synthesis of poly(ethylene glycol)-block-poly(N-isopropyl acrylamide-co-N-(4-hydroxyphenethyl) acrylamide) diblock copolymer PEG-b-P(NIPAAm-co-NHPAAm) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The diblock copolymer was then self-assembled into non-cross-linked (NCL) micelles upon heating above the lower critical solution temperature (LCST), and subsequently cross-linked using horseradish peroxidase (HRP) and hydrogen peroxide (H2O2) as enzyme and oxidant. The characterization of the diblock copolymer and micelles were studied by NMR, DLS, UV-vis, and fluorescence spectroscopy. The fluorescence study reveals that the cross-linking process endows the micelles with much lower critical micelle concentration (CMC). In addition, the drug release study shows that the CCL micelles have lower release amount of doxorubicin (DOX) than the NCL micelles due to the enhanced stability of the CCL micelles by core cross-linking process. Copyright © 2014 Elsevier B.V. All rights reserved.
Lightweight Thermal Insulation for a Liquid-Oxygen Tank
NASA Technical Reports Server (NTRS)
Willen, G. Scott; Lock, Jennifer; Nieczkoski, Steve
2005-01-01
A proposed lightweight, reusable thermal-insulation blanket has been designed for application to a tank containing liquid oxygen, in place of a non-reusable spray-on insulating foam. The blanket would be of the multilayer-insulation (MLI) type and equipped with a pressure-regulated nitrogen purge system. The blanket would contain 16 layers in two 8-layer sub-blankets. Double-aluminized polyimide 0.3 mil (.0.008 mm) thick was selected as a reflective shield material because of its compatibility with oxygen and its ability to withstand ionizing radiation and high temperature. The inner and outer sub-blanket layers, 1 mil (approximately equals 0.025 mm) and 3 mils (approximately equals 0.076 mm) thick, respectively, would be made of the double-aluminized polyimide reinforced with aramid. The inner and outer layers would provide structural support for the more fragile layers between them and would bear the insulation-to-tank attachment loads. The layers would be spaced apart by lightweight, low-thermal-conductance netting made from polyethylene terephthalate.
Morita, Daigo; Seki, Taisuke; Higuchi, Yoshitoshi; Takegami, Yasuhiko; Ishiguro, Naoki
2017-12-01
This study aimed at investigating differences in femoral head penetration between highly cross-linked polyethylene (HXLPE) cemented sockets and uncemented liners during 5 years postoperatively. Ninety-six patients (106 hips) with a mean age of 64.4 (range, 35-83) years underwent total hip arthroplasty using a HXLPE cemented socket or liner and were respectively divided into cemented (35 patients [37 hips]) and uncemented (61 patients [69 hips]) groups. Femoral head penetrations were evaluated on both anteroposterior (AP)-view and Lauenstein-view radiographs, and mean polyethylene (PE) wear rates were calculated based on femoral head penetration from 2 to 5 years. Multivariate analyses were performed to assess risk factors for PE wear. At 5 years postoperatively, the cemented and uncemented groups exhibited proximal direction femoral head penetrations of 0.103 mm and 0.124 mm (P = .226) and anterior direction penetrations of 0.090 mm and 0.151 mm (P = .002), respectively. The corresponding mean PE wear rates were 0.004 mm/y and 0.009 mm/y in the AP-view (P = .286) and 0.005 mm/y and 0.012 mm/y in the Lauenstein-view (P = .168), respectively. Left-side operation and high activity were independent risk factors for PE wear on AP-view. When HXLPE was used, all mean PE wear rates were very low and those of cemented sockets and uncemented liners were very similar. PE particle theory suggests that the occurrence of osteolysis and related aseptic loosening might consequently decrease. Copyright © 2017 Elsevier Inc. All rights reserved.
Takahashi, Yasuhito; Shishido, Takaaki; Yamamoto, Kengo; Masaoka, Toshinori; Kubo, Kosuke; Tateiwa, Toshiyuki; Pezzotti, Giuseppe
2015-02-01
Plastic deformation is an unavoidable event in biomedical polymeric implants for load-bearing application during long-term in-vivo service life, which involves a mass transfer process, irreversible chain motion, and molecular reorganization. Deformation-induced microstructural alterations greatly affect mechanical properties and durability of implant devices. The present research focused on evaluating, from a molecular physics viewpoint, the impact of externally applied strain (or stress) in ultra-high molecular weight polyethylene (UHMWPE) prostheses, subjected to radiation cross-linking and subsequent remelting for application in total hip arthroplasty (THA). Two different types of commercial acetabular liners, which belong to the first-generation highly cross-linked UHMWPE (HXLPE), were investigated by means of confocal/polarized Raman microprobe spectroscopy. The amount of crystalline region and the spatial distribution of molecular chain orientation were quantitatively analyzed according to a combined theory including Raman selection rules for the polyethylene orthorhombic structure and the orientation distribution function (ODF) statistical approach. The structurally important finding was that pronounced recrystallization and molecular reorientation increasingly appeared in the near-surface regions of HXLPE liners with increasing the amount of plastic (compressive) deformation stored in the microstructure. Such molecular rearrangements, occurred in response to external strains, locally increase surface cross-shear (CS) stresses, which in turn trigger microscopic wear processes in HXLPE acetabular liners. Thus, on the basis of the results obtained at the molecular scale, we emphasize here the importance of minimizing the development of irrecoverable deformation strain in order to retain the pristine and intrinsically high wear performance of HXLPE components. Copyright © 2014 Elsevier Ltd. All rights reserved.
Pedron, S; Peinado, C; Bosch, P; Benton, J A; Anseth, K S
2011-01-01
High-throughput methods allow rapid examination of parameter space to characterize materials and develop new polymeric formulations for biomaterials applications. One limitation is the difficulty of preparing libraries and performing high-throughput screening with conventional instrumentation and sample preparation. Here, we describe the fabrication of substrate materials with controlled gradients in composition by a rapid method of micromixing followed by a photopolymerization reaction. Specifically, poly(ethylene glycol) dimethacrylate was copolymerized with a hyperbranched multimethacrylate (P1000MA or H30MA) in a gradient manner. The extent of methacrylate conversion and the final network composition were determined by near-infrared spectroscopy, and mechanical properties were measured by nanoindentation. A relationship was observed between the elastic modulus and network crosslinking density. Roughness and hydrophilicity were increased on surfaces with a higher concentration of P1000MA. These results likely relate to a phase segregation process of the hyperbranched macromer that occurs during the photopolymerization reaction. On the other hand, the decrease in the final conversion in H30MA polymerization reactions was attributed to the lower termination rate as a consequence of the softening of the network. Valvular interstitial cell attachment was evaluated on these gradient substrates as a demonstration of studying cell morphology as a function of the local substrate properties. Data revealed that the presence of P1000MA affects cell–material interaction with a higher number of adhered cells and more cell spreading on gradient regions with a higher content of the multifunctional crosslinker. PMID:21105168
Wang, Zhigao; Zhang, Xinghai; Wang, Fangqiang; Lan, Xinsheng; Zhou, Yiqian
2016-01-01
In order to analyze the cracking and aging reason of the silicone rubber current transformer (CT) insulation bushing used for 8 years from a 500 kV alternating current substation, characteristics including Fourier transform infrared (FTIR) spectroscopy, mechanical properties analysis, hardness, and thermo gravimetric analysis have been carried out. The FTIR results indicated that the external surface of the silicone rubber CT insulation bushing suffered from more serious aging than the internal part, fracture of side chain Si-C bond was much more than the backbone. Mechanical properties and thermal stability results illustrated that the main aging reasons were the breakage of side chain Si-C bond and the excessive cross-linking reaction of the backbone. This study can provide valuable basis for evaluating degradation mechanism and aging state of the silicone rubber insulation bushing in electric power field.
Guerra, Alberto Daniel; Rose, Warren E; Hematti, Peiman; Kao, W John
2017-03-15
Mesenchymal stromal/stem cells (MSCs) have demonstrated pro-healing properties including an anti-inflammatory cytokine profile and the promotion of angiogenesis via expression of growth factors in pre-clinical models. MSCs encapsulated in poly(ethylene glycol) diacrylate (PEGdA) and thiolated gelatin poly(ethylene glycol) (Gel-PEG-Cys) crosslinked hydrogels have led to controlled cellular presentation at wound sites with favorable wound healing outcomes. However, the therapeutic potential of MSC-loaded hydrogels may be limited by non-specific protein adsorption on the delivery matrix that could facilitate the initial adhesion of microorganisms and subsequent virulent biofilm formation. Antimicrobials loaded concurrently in the hydrogels with MSCs could reduce microbial bioburden and promote healing, but the antimicrobial effect on the MSC wound healing capacity and the antibacterial efficacy of the hydrogels is unknown. We demonstrate that minocycline specifically induces a favorable change in MSC migration capacity, proliferation, gene expression, extracellular matrix (ECM) attachment, and adhesion molecule and growth factor release with subsequent increased angiogenesis. We then demonstrate that hydrogels loaded with MSCs, minocycline, vancomycin, and linezolid can significantly decrease bacterial bioburden. Our study suggests that minocycline can serve as a dual mechanism for the regenerative capacity of MSCs and the reduction of bioburden in triple antimicrobial-loaded hydrogels. Wound healing is a complex biological process that can be hindered by bacterial infection, excessive inflammation, and inadequate microvasculature. In this study, we develop a new formulation of poly(ethylene glycol) diacrylate and thiolated gelatin poly(ethylene glycol) crosslinked hydrogels loaded with minocycline, vancomycin, linezolid, and mesenchymal stromal/stem cells that induces a favorable wound healing phenotype in mesenchymal stromal/stem cells and prevents bacterial bioburden on the hydrogel. This combinatorial approach to biomaterial development has the potential to impact wound healing for contaminated full thickness cutaneous wounds. Copyright © 2017. Published by Elsevier Ltd.
Optimisation of multi-layer rotationally moulded foamed structures
NASA Astrophysics Data System (ADS)
Pritchard, A. J.; McCourt, M. P.; Kearns, M. P.; Martin, P. J.; Cunningham, E.
2018-05-01
Multi-layer skin-foam and skin-foam-skin sandwich constructions are of increasing interest in the rotational moulding process for two reasons. Firstly, multi-layer constructions can improve the thermal insulation properties of a part. Secondly, foamed polyethylene sandwiched between solid polyethylene skins can increase the mechanical properties of rotationally moulded structural components, in particular increasing flexural properties and impact strength (IS). The processing of multiple layers of polyethylene and polyethylene foam presents unique challenges such as the control of chemical blowing agent decomposition temperature, and the optimisation of cooling rates to prevent destruction of the foam core; therefore, precise temperature control is paramount to success. Long cooling cycle times are associated with the creation of multi-layer foam parts due to their insulative nature; consequently, often making the costs of production prohibitive. Devices such as Rotocooler®, a rapid internal mould water spray cooling system, have been shown to have the potential to significantly decrease cooling times in rotational moulding. It is essential to monitor and control such devices to minimise the warpage associated with the rapid cooling of a moulding from only one side. The work presented here demonstrates the use of threaded thermocouples to monitor the polymer melt in multi-layer sandwich constructions, in order to analyse the cooling cycle of multi-layer foamed structures. A series of polyethylene skin-foam test mouldings were produced, and the effect of cooling medium on foam characteristics, mechanical properties, and process cycle time were investigated. Cooling cycle time reductions of 45%, 26%, and 29% were found for increasing (1%, 2%, and 3%) chemical blowing agent (CBA) amount when using internal water cooling technology from ˜123°C compared with forced air cooling (FAC). Subsequently, a reduction of IS for the same skin-foam parts was found to be 1%, 4%, and 16% compared with FAC.
In-Situ Air Sparaing: Engineering and Design
2008-01-31
Construction Materials. Although PVC casing is commonly used, flexible or rigid polyethylene pipe may be more efficient for certain excavation methods, such as...depth, etc.) Piping insulation/ heat tape installed Piping flushed/cleaned/pressure tested Subsurface as-built equipment...4-4 Figure 4-2 Pilot-Scale Piping and Instrumentation Diagram
Multiple Ion Implantation Effects on Wear and Wet Ability of Polyethylene Based Polymers
NASA Astrophysics Data System (ADS)
Torrisi, L.; Visco, A. M.; Campo, N.
2004-10-01
Polyethylene based polymers were ion implanted with multiple irradiations of different ions (N+, Ar+ and Kr+) at energies between 30 keV and 300 keV and doses ranging between 1013 and 1016 ions/cm2. The ion implantation dehydrogenises the polyethylene inducing cross-link effects in the residual polymer carbons. At high doses the irradiated surface show properties similar to graphite surfaces. The depth of the modified layers depends on the ion range in polyethylene at the incident ion energy. The chemical modification depends on the implanted doses and on the specie of the incident ions. A "pin-on-disc" machine was employed to measure the polymer wear against AISI-316 L stainless steel. A "contact-angle-test" machine was employed to measure the wet ability of the polymer surface for 1 μl pure water drop. Measurements demonstrate that the multiple ion implantation treatments decrease the surface wear and the surface wetting and produce a more resistant polymer surface. The properties of the treated surfaces improves the polymer functionality for many bio-medical applications, such as those relative to the polyethylene friction discs employed in knee and hip prosthesis joints. The possibility to use multiply ion implantations of polymers with traditional ion implanters and with laser ion sources producing plasmas is investigated.
NASA Astrophysics Data System (ADS)
Zhang, Jinghui; Huang, Zhiwei; Liu, Dan
2017-12-01
Polymer thin films are generally employed as coatings on implants to prevent protein adsorption. Polymer chain mobility and surface softness have been found to contribute to the protein resistance, but also bring film instability in a liquid protein medium. We investigated the protein resistance ability of three low-Tg polymers, including hydrophobic polymers polyisoprene (PI), poly(n-butyl methacrylate) (PnBMA) and hydrophilic polyethylene oxide (PEO), by overcoming the instability issue with crosslinking. We found that the Tgs of PI and PEO can be increased to around 0 °C after crosslinking. The remained strong chain mobility of both films can still resist protein adsorption regardless the hydrophobicity, yet greatly increases the film stability under an aqueous circumstance. The PnBMA film increased its Tg to around room temperature after crosslinking, which deteriorated the protein-resistance ability having the surface covered by BSA molecules. Our results support that the chain mobility of a polymer film plays an important role in resisting protein adsorption due to the increased entropy associated with more mobile polymer chains. By tune the degree of crosslinking, the stability of polymer in aqueous environment can be increased while the protein resistant ability can be remained. Our results provide a new strategy to design polymer materials for effective antifouling.
Photo-Patterned Ion Gel Electrolyte-Gated Thin Film Transistors
NASA Astrophysics Data System (ADS)
Choi, Jae-Hong; Gu, Yuanyan; Hong, Kihyun; Frisbie, C. Daniel; Lodge, Timothy P.
2014-03-01
We have developed a novel fabrication route to pattern electrolyte thin films in electrolyte-gated transistors (EGTs) using a chemically crosslinkable ABA-triblock copolymer ion gel. In the self-assembly of poly[(styrene-r-vinylbenzylazide)-b-ethylene oxide-b-(styrene-r-vinylbenzylazide)] (SOS-N3) triblock copolymer and the ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]), the azide groups of poly(styrene-r-vinylbenzylazide) (PS-N3) end-blocks in the cores can be chemically cross-linked via UV irradiation (λ = 254 nm). Impedance spectroscopy and small-angle X-ray scattering confirmed that ion transport and microstructure of the ion gel are not affected by UV cross-linking. Using this chemical cross-linking strategy, we demonstrate a photo-patterning of ion gels through a patterned mask and the fabricated electrolyte-gated thin film transistors with photo-patterned ion gels as high-capacitance gate insulators exhibited high device performance (low operation voltages and high on/off current ratios).
Pourrahimi, Amir Masoud; Pallon, Love K H; Liu, Dongming; Hoang, Tuan Anh; Gubanski, Stanislaw; Hedenqvist, Mikael S; Olsson, Richard T; Gedde, Ulf W
2016-06-15
The use of MgO nanoparticles in polyethylene for cable insulation has attracted considerable interest, although in humid media the surface regions of the nanoparticles undergo a conversion to a hydroxide phase. A facile method to obtain MgO nanoparticles with a large surface area and remarkable inertness to humidity is presented. The method involves (a) low temperature (400 °C) thermal decomposition of Mg(OH)2, (b) a silicone oxide coating to conceal the nanoparticles and prevent interparticle sintering upon exposure to high temperatures, and (c) heat treatment at 1000 °C. The formation of the hydroxide phase on these silicone oxide-coated MgO nanoparticles after extended exposure to humid air was assessed by thermogravimetry, infrared spectroscopy, and X-ray diffraction. The nanoparticles showed essentially no sign of any hydroxide phase compared to particles prepared by the conventional single-step thermal decomposition of Mg(OH)2. The moisture-resistant MgO nanoparticles showed improved dispersion and interfacial adhesion in the LDPE matrix with smaller nanosized particle clusters compared with conventionally prepared MgO. The addition of 1 wt % moisture-resistant MgO nanoparticles was sufficient to decrease the conductivity of polyethylene 30 times. The reduction in conductivity is discussed in terms of defect concentration on the surface of the moisture-resistant MgO nanoparticles at the polymer/nanoparticle interface.
Injectable Absorbable Ocular Inserts for Controlled Drug Delivery
1997-07-01
conjunctiva for prolonged delivery of drugs to the anterior region of the eye (Gwon & Meadows, 1992). The dosage system was an elliptically shaped unit...1979) have reviewed many other gel formers which are available for preparing pharmaceutical gels. A.3.4.1. Hydrogels -- Hydrogels are materials which...denoted as hydrogels (or aquagels). Hydrogels based on crosslinked polymeric chains of methoxy poly(ethylene glycol) monomethacrylate having variable
NASA Astrophysics Data System (ADS)
Marković, G.; Marinović-Cincović, M.; Tanasić, Lj.; Jovanović, V.; Samaržija-Jovanović, S.; Vukić, N.; Budinski-Simendić, J.
2011-12-01
The goal of this work was to study gamma irradiation ageing of rubber blends based on acrylonitrile butadiene rubber (NBR) and chlorosulphonated polyethylene rubber (CSM) reinforced by silica nano particles. The NBR/CSM compounds (50: 50, w/w) filled with different content of filler (0-100 phr) were crosslinked by sulfur. The vulcanization characteristics were assessed using the rheometer with an oscillating disk. The vulcanizates were prepared in a hydraulic press. The obtained materials were exposed to the different irradiation doses (100, 200, 300 and 400 kGy). The mechanical properties (hardness, modulus at 100% elongation, tensile strength and elongation at break) and swelling numbers were assessed before and after gamma irradiation ageing.
Electrospinning pectin-based nanofibers: a parametric and cross-linker study
NASA Astrophysics Data System (ADS)
McCune, Devon; Guo, Xiaoru; Shi, Tong; Stealey, Samuel; Antrobus, Romare; Kaltchev, Matey; Chen, Junhong; Kumpaty, Subha; Hua, Xiaolin; Ren, Weiping; Zhang, Wujie
2018-02-01
Pectin, a natural biopolymer mainly derived from citrus fruits and apple peels, shows excellent biodegradable and biocompatible properties. This study investigated the electrospinning of pectin-based nanofibers. The parameters, pectin:PEO (polyethylene oxide) ratio, surfactant concentration, voltage, and flow rate, were studied to optimize the electrospinning process for generating the pectin-based nanofibers. Oligochitosan, as a novel and nonionic cross-liker of pectin, was also researched. Nanofibers were characterized by using AFM, SEM, and FTIR spectroscopy. The results showed that oligochitosan was preferred over Ca2+ because it cross-linked pectin molecules without negatively affecting the nanofiber morphology. Moreover, oligochitosan treatment produced a positive surface charge of nanofibers, determined by zeta potential measurement, which is desired for tissue engineering applications.
Study on the PTC/NTC effect of carbon black-filled polymer composites
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tang, Hao; Chen, Xinfang; Luo, Yunxia
1995-12-01
In this work, the effect of processing condition and radiation-crosslinking on the electrical and dynamic behaviors of carbon black filled low density polyethylene (LDPE) composites were investigated. Compared with the solution counterpart, the mechanical composites have a strong PTC effect and a great dynamic elastic mold, which results from the strong interaction between carbon black and LDPE. The experiment result shows that the NTC effect is caused by the decrease of elastic mold of LDPE at high temperature, and it can be declined significantly by radiation-crosslinking. We conclude that the strong interaction between polymer and carbon black is essentially importantmore » for composites to have a great PTC intensity good electrical reproducibility and high dynamic elastic sold.« less
Synthetically Simple, Highly Resilient Hydrogels
Cui, Jun; Lackey, Melissa A.; Madkour, Ahmad E.; Saffer, Erika M.; Griffin, David M.; Bhatia, Surita R.; Crosby, Alfred J.; Tew, Gregory N.
2014-01-01
Highly resilient synthetic hydrogels were synthesized by using the efficient thiol-norbornene chemistry to cross-link hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) polymer chains. The swelling and mechanical properties of the hydrogels were well-controlled by the relative amounts of PEG and PDMS. In addition, the mechanical energy storage efficiency (resilience) was more than 97% at strains up to 300%. This is comparable with one of the most resilient materials known: natural resilin, an elastic protein found in many insects, such as in the tendons of fleas and the wings of dragonflies. The high resilience of these hydrogels can be attributed to the well-defined network structure provided by the versatile chemistry, low cross-link density, and lack of secondary structure in the polymer chains. PMID:22372639
Fully synthetic taped insulation cables
Forsyth, E.B.; Muller, A.C.
1983-07-15
The present invention is a cable which, although constructed from inexpensive polyolefin tapes and using typical impregnating oils, furnishes high voltage capability up to 765 kV, and has such excellent dielectric characteristics and heat transfer properties that it is capable of operation at capacities equal to or higher than presently available cables at a given voltage. This is accomplished by using polyethylene, polybutene or polypropylene insulating tape which has been specially processed to attain properties which are not generally found in these materials, but are required for their use in impregnated electrical cables. Chief among these properties is compatibility with impregnating oil.
Nicodemus, G D; Skaalure, S C; Bryant, S J
2011-02-01
While designing poly(ethylene glycol) hydrogels with high moduli suitable for in situ placement is attractive for cartilage regeneration, the impact of a tighter crosslinked structure on the organization and deposition of the matrix is not fully understood. The objectives of this study were to characterize the composition and spatial organization of new matrix as a function of gel crosslinking and study its impact on chondrocytes in terms of anabolic and catabolic gene expression and catabolic activity. Bovine articular chondrocytes were encapsulated in hydrogels with three crosslinking densities (compressive moduli 60, 320 and 590 kPa) and cultured for 25 days. Glycosaminoglycan production increased with culture time and was greatest in the gels with lowest crosslinking. Collagens II and VI, aggrecan, link protein and decorin were localized to pericellular regions in all gels, but their presence decreased with increasing gel crosslinking. Collagen II and aggrecan expression were initially up-regulated in gels with higher crosslinking, but increased similarly up to day 15. Matrix metalloproteinase (MMP)-1 and MMP-13 expression were elevated (∼25-fold) in gels with higher crosslinking throughout the study, while MMP-3 was unaffected by gel crosslinking. The presence of aggrecan and collagen degradation products confirmed MMP activity. These findings indicate that chondrocytes synthesized the major cartilage components within PEG hydrogels, however, gel structure had a significant impact on the composition and spatial organization of the new tissue and on how chondrocytes responded to their environment, particularly with respect to their catabolic expression. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Hanay, Saltuk B; Ritzen, Bas; Brougham, Dermot; Dias, Aylvin A; Heise, Andreas
2017-07-01
Highly efficient functionalization and cross-linking of polypeptides is achieved via tyrosine-triazolinedione (TAD) conjugation chemistry. The feasibility of the reaction is demonstrated by the reaction of 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) with tyrosine containing block copolymer poly(ethylene glycol)-Tyr 4 as well as a statistical copolymer of tyrosine and lysine (poly(Lys 40 -st-Tyr 10 )) prepared form N-carboxyanhydride polymerization. Selective reaction of PTAD with the tyrosine units is obtained and verified by size exclusion chromatography and NMR spectroscopy. Moreover, two monofunctional and two difunctional TAD molecules are synthesized. It is found that their stability in the aqueous reaction media significantly varied. Under optimized reaction conditions selective functionalization and cross-linking, yielding polypeptide hydrogels, can be achieved. TAD-mediated conjugation can offer an interesting addition in the toolbox of selective (click-like) polypeptide conjugation methodologies as it does not require functional non-natural amino acids. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
ZnO thin-film transistors with a polymeric gate insulator built on a polyethersulfone substrate
NASA Astrophysics Data System (ADS)
Hyung, Gun Woo; Park, Jaehoon; Koo, Ja Ryong; Choi, Kyung Min; Kwon, Sang Jik; Cho, Eou Sik; Kim, Yong Seog; Kim, Young Kwan
2012-03-01
Zinc oxide (ZnO) thin-film transistors (TFTs) with a cross-linked poly(vinyl alcohol) (c-PVA) insulator are fabricated on a polyethersulfone substrate. The ZnO film, formed by atomic layer deposition, shows a polycrystalline hexagonal structure with a band gap energy of about 3.37 eV. The fabricated ZnO TFT exhibits a field-effect mobility of 0.38 cm2/Vs and a threshold voltage of 0.2 V. The hysteresis of the device is mainly caused by trapped electrons at the c-PVA/ZnO interface, whereas the positive threshold voltage shift occurs as a consequence of constant positive gate bias stress after 5000 s due to an electron injection from the ZnO film into the c-PVA insulator.
Thermal and catalytic degradation of high and low density polyethylene into fuel oil
DOE Office of Scientific and Technical Information (OSTI.GOV)
Uddin, Azhar; Koizumi, Kazuo; Sakata, Yusaku
1996-12-31
The degradation of four different types of polyethylene (PE) namely high density PE (HDPE), low density PE (LDPE), linear low density PE (LLDPE), and cross-linked PE (XLPE) was carried out at 430 {degrees}C by batch operation using silica-alumina as a solid acid catalyst and thermally without any catalyst. For thermal degradation, both HDPE and XLPE produced significant amount of wax-like compounds and the yield of liquid products were lower than that of LDPE and LLDPE. LDPE and LLDPE also produced small amount of wax-like compounds. Thus the structure of the degrading polymers influenced the product yields. The liquid products frommore » thermal degradation were broadly distributed in the carbon fraction of n-C{sub 5} to n-C{sub 25} (boiling point range, 36-405 C). With silica-alumina, the polyethylenes were converted to liquid products with high yields (77-83 wt%) and without any wax production. The liquid products were distributed in the range of n-C{sub 5} to n-C{sub 20} (Mostly C{sub 5}-C{sub 12}). Solid acid catalyst indiscriminately degraded the various types of polyethylene into light fuel oil. 5 refs., 4 figs., 1 tab.« less
Novel active stabilization technology in highly crosslinked UHMWPEs for superior stability
NASA Astrophysics Data System (ADS)
Oral, Ebru; Neils, Andrew L.; Wannomae, Keith K.; Muratoglu, Orhun K.
2014-12-01
Radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is the bearing of choice in joint arthroplasty. The demands on the longevity of this polymer are likely to increase with the recently advancing deterioration of the performance of alternative metal-on-metal implants. Vitamin E-stabilized, cross-linked UHMWPEs are considered the next generation of improved UHMWPE bearing surfaces for improving the oxidation resistance of the polymer. It was recently discovered that in the absence of radiation-induced free radicals, lipids absorbed into UHMWPE from the synovial fluid can initiate oxidation and result in new free radical-mediated oxidation mechanisms. In the presence of radiation-induced free radicals, it is possible for the polymer to oxidize through both existing free radicals at the time of implantation and through newly formed free radicals in vivo. Thus, we showed that reducing the radiation-induced free radicals in vitamin E-stabilized UHMWPE would increase its oxidative stability and presumably lead to improved longevity. We describe mechanical annealing and warm irradiation of irradiated vitamin E blends as novel methods to eliminate 99% of radiation-induced free radicals without sacrificing crystallinity. These are significant improvements in the processing of highly cross-linked UHMWPE for joint implants with improved longevity.
Lacoste, Clément; El Hage, Roland; Bergeret, Anne; Corn, Stéphane; Lacroix, Patrick
2018-03-15
Alginate derived from seaweed is a natural polysaccharide able to form stable gel through carbohydrate functional groups largely used in the food and pharmaceutical industry. This article deals with the use of sodium alginate as an adhesive binder for wood fibres/textile waste fibres biocomposites. Several aldehyde-based crosslinking agents (glyoxal, glutaraldehyde) were compared for various wood/textile waste ratios (100/0, 50/50, 60/40, 70/30 and 0/100 in weight). The fully biomass derived composites whose properties are herewith described satisfy most of the appropriate requirements for building materials. They are insulating with a thermal conductivity in the range 0.078-0.089 W/m/K for an average density in the range 308-333 kg/m3 according to the biocomposite considered. They are semi-rigid with a maximal mechanical strength of 0.84 MPa under bending and 0.44 MPa under compression for 60/40 w/w wood/textile waste biocomposites with a glutaraldehyde crosslinking agent. Copyright © 2017 Elsevier Ltd. All rights reserved.
Crosslinked polymer nanoparticles containing single conjugated polymer chains
NASA Astrophysics Data System (ADS)
Ponzio, Rodrigo A.; Marcato, Yésica L.; Gómez, María L.; Waiman, Carolina V.; Chesta, Carlos A.; Palacios, Rodrigo E.
2017-06-01
Conjugated polymer nanoparticles are widely used in fluorescent labeling and sensing, as they have mean radii between 5 and 100 nm, narrow size dispersion, high brightness, and are photochemically stable, allowing single particle detection with high spatial and temporal resolution. Highly crosslinked polymers formed by linking individual chains through covalent bonds yield high-strength rigid materials capable of withstanding dissolution by organic solvents. Hence, the combination of crosslinked polymers and conjugated polymers in a nanoparticulated material presents the possibility of interesting applications that require the combined properties of constituent polymers and nanosized dimension. In the present work, F8BT@pEGDMA nanoparticles composed of poly(ethylene glycol dimethacrylate) (pEGDMA; a crosslinked polymer) and containing the commercial conjugated polymer poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) were synthesized and characterized. Microemulsion polymerization was applied to produce F8BT@pEDGMA particles with nanosized dimensions in a ∼25% yield. Photophysical and size distribution properties of F8BT@pEDGMA nanoparticles were evaluated by various methods, in particular single particle fluorescence microscopy techniques. The results demonstrate that the crosslinking/polymerization process imparts structural rigidity to the F8BT@pEDGMA particles by providing resistance against dissolution/disintegration in organic solvents. The synthesized fluorescent crosslinked nanoparticles contain (for the most part) single F8BT chains and can be detected at the single particle level, using fluorescence microscopy, which bodes well for their potential application as molecularly imprinted polymer fluorescent nanosensors with high spatial and temporal resolution.
Technological parameters of welding of branch saddles to polyethylene pipes at low temperatures
NASA Astrophysics Data System (ADS)
Starostin, N. P.; Vasilieva, M. A.
2017-12-01
The present paper outlines a procedure for determination of dynamics of the temperature field during the welding of the branch saddle to the polyethylene gas pipeline at ambient temperatures below the normative. The analysis is accomplished by the finite element method with the heat of the phase transition taken into account. Methods of the visualization of data sets reveal the possibility of controlling the thermal process by preheating and thermal insulation during welding of the branch saddle to the pipe at low temperatures and the possibility of obtaining the dynamics of the temperature field at which a high-quality welded joint is formed.
NASA Astrophysics Data System (ADS)
Yang, Zhang; Renping, Zhang; Weihua, Han; Jian, Liu; Xiang, Yang; Ying, Wang; Chian Chiu, Li; Fuhua, Yang
2009-11-01
A two-step exposure method to effectively reduce the proximity effect in fabricating nanometer-spaced nanopillars is presented. In this method, nanopillar patterns on poly-methylmethacrylate (PMMA) were partly cross-linked in the first-step exposure. After development, PMMA between nanopillar patterns was removed, and hence the proximity effect would not take place there in the subsequent exposure. In the second-step exposure, PMMA masks were completely cross-linked to achieve good resistance in inductively coupled plasma etching. Accurate pattern transfer of rows of nanopillars with spacing down to 40 nm was realized on a silicon-on-insulator substrate.
2015-10-01
shown in Fig. 1a, the prepolymer mixture was sandwiched between photo mask and glass slide. Microdiscs were fabricated on the glass substrate through...polymerization of the prepolymer mixture and the acrylated silane under UV exposure. To achieve the more stable microdiscs for peptide synthesis, the...composition of prepolymer mixture was changed to PEG (Polyethylene Glycol)-diacrylate, crosslinker, photo initiator, 2-aminoethylmethacrylate, water
Gioe, Terence J; Sharma, Amit; Tatman, Penny; Mehle, Susan
2011-01-01
Numerous joint implant options of varying cost are available to the surgeon, but it is unclear whether more costly implants add value in terms of function or longevity. We evaluated registry survival of higher-cost "premium" knee and hip components compared to lower-priced standard components. Premium TKA components were defined as mobile-bearing designs, high-flexion designs, oxidized-zirconium designs, those including moderately crosslinked polyethylene inserts, or some combination. Premium THAs included ceramic-on-ceramic, metal-on-metal, and ceramic-on-highly crosslinked polyethylene designs. We compared 3462 standard TKAs to 2806 premium TKAs and 868 standard THAs to 1311 premium THAs using standard statistical methods. The cost of the premium implants was on average approximately $1000 higher than the standard implants. There was no difference in the cumulative revision rate at 7-8 years between premium and standard TKAs or THAs. In this time frame, premium implants did not demonstrate better survival than standard implants. Revision indications for TKA did not differ, and infection and instability remained contributors. Longer followup is necessary to demonstrate whether premium implants add value in younger patient groups. Level III, therapeutic study. See Guidelines for Authors for a complete description of levels of evidence.
Nebergall, Audrey K; Greene, Meridith E; Rubash, Harry; Malchau, Henrik; Troelsen, Anders; Rolfson, Ola
2016-09-01
The objective of this 13-year prospective evaluation of highly cross-linked ultra high molecular weight polyethylene (HXLPE) was to (1) assess the long-term wear of HXLPE articulating with 2 femoral head sizes using radiostereometric analysis (RSA) and to (2) determine if osteolysis is a concern with this material through the use of plain radiographs and computerized tomography (CT). All patients received a Longevity HXLPE liner with tantalum beads and either a 28-mm or 36-mm femoral head. Twelve patients (6 in each head size group) agreed to return for 13-year RSA, plain radiograph, and CT follow-up. The 1-year and 13-year plain radiographs as well as the CT scans were analyzed for the presence of osteolysis. The 13-year mean ± standard error steady-state wear was 0.05 ± 0.02 mm with no significant increase over time or between the 2 head size groups. Two patients' CT scans showed radiolucent regions in the acetabulum of 4.51 cm(3) and 11.25 cm(3), respectively. In one patient, this area corresponded to a partially healed degenerative cyst treated with autograft during surgery. The second patient had an acetabular protrusio treated with autograft, and the CT scan revealed areas of remodeling of this graft. One patient's 13-year plain radiographs showed evidence of cup loosening and linear radiolucencies in zones 2 and 3. There was no evidence of significant wear over time using RSA. The CT scans did not show evidence of osteolysis due to wear particles. These results suggest that this material has reduced wear compared to conventional polyethylene, irrespective of head size. Copyright © 2016 Elsevier Inc. All rights reserved.
Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho
2017-10-04
We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.
Slide-Ring Materials Using Cyclodextrin.
Ito, Kohzo
2017-01-01
We have recently synthesized slide-ring materials using cyclodextrin by cross-linking polyrotaxanes, a typical supramolecule. The slide-ring materials have polymer chains with bulky end groups topologically interlocked by figure-of-eight shaped junctions. This indicates that the cross-links can pass through the polymer chains similar to pulleys to relax the tension of the backbone polymer chains. The slide-ring materials also differ from conventional polymers in that the entropy of rings affects the elasticity. As a result, the slide-ring materials show quite small Young's modulus not proportional to the cross-linking density. This concept can be applied to a wide variety of polymeric materials as well as gels. In particular, the slide-ring materials show remarkable scratch-proof properties for coating materials for automobiles, cell phones, mobile computers, and so on. Further current applications include vibration-proof insulation materials for sound speakers, highly abrasive polishing media, dielectric actuators, and so on.
Polyimide aerogels cross-linked through amine functionalized polyoligomeric silsesquioxane.
Guo, Haiquan; Meador, Mary Ann B; McCorkle, Linda; Quade, Derek J; Guo, Jiao; Hamilton, Bart; Cakmak, Miko; Sprowl, Guilherme
2011-02-01
We report the first synthesis of polyimide aerogels cross-linked through a polyhedral oligomeric silsesquioxane, octa(aminophenyl)silsesquioxane (OAPS). Gels formed from polyamic acid solutions of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), bisaniline-p-xylidene (BAX) and OAPS were chemically imidized and dried using supercritical CO(2) extraction to give aerogels having density around 0.1 g/cm(3). The aerogels are greater than 90 % porous, have high surface areas (230 to 280 m(2)/g) and low thermal conductivity (14 mW/m-K at room temperature). Notably, the polyimide aerogels cross-linked with OAPS have higher modulus than polymer reinforced silica aerogels of similar density and can be fabricated as both monoliths and thin films. Thin films of the aerogel are flexible and foldable making them an ideal insulation for space suits, and inflatable structures for habitats or decelerators for planetary re-entry, as well as more down to earth applications.
Lee, Hyun Jin; Bae, Younsoo
2013-02-01
To identify the effects of cross-linkers and drug-binding linkers on physicochemical and biological properties of polymer nanoassembly drug carriers. Four types of polymer nanoassemblies were synthesized from poly(ethylene glycol)-poly(aspartate) [PEG-p(Asp)] block copolymers: self-assembled nanoassemblies (SNAs) and cross-linked nanoassemblies (CNAs) to each of which an anticancer drug doxorubicin (DOX) was loaded by either physical entrapment or chemical conjugation (through acid-sensitive hydrazone linkers). Drug loading in nanoassemblies was 27 ~ 56% by weight. The particle size of SNA changed after drug and drug-binding linker entrapment (20 ~ 100 nm), whereas CNAs remained 30 ~ 40 nm. Drug release rates were fine-tunable by using amide cross-linkers and hydrazone drug-binding linkers in combination. In vitro cytotoxicity assays using a human lung cancer A549 cell line revealed that DOX-loaded nanoassemblies were equally potent as free DOX with a wide range of drug release half-life (t(1/2) = 3.24 ~ 18.48 h, at pH 5.0), but 5 times less effective when t(1/2) = 44.52 h. Nanoassemblies that incorporate cross-linkers and drug-binding linkers in combination have pharmaceutical advantages such as uniform particle size, physicochemical stability, fine-tunable drug release rates, and maximum cytotoxicity of entrapped drug payloads.
NASA Astrophysics Data System (ADS)
Sheng, Haibo; Zhang, Yan; Wang, Bibo; Yu, Bin; Shi, Yongqian; Song, Lei; Kundu, Chanchal Kumar; Tao, Youji; Jie, Ganxin; Feng, Hao; Hu, Yuan
2017-04-01
Microencapsulated ammonium polyphosphate (MCAPP) in combination with polyester polyurethane (TPU) was used to flame retardant ethylene-vinyl acetate copolymer (EVA). The EVA composites with different irradiation doses were immersed in hot water (80 °C) to accelerate ageing process. The microencapsulation and irradiation dose ensured positive impacts on the properties of the EVA composites in terms of better dimensional stability and flame retardant performance. The microencapsulation of APP could lower its solubility in water and the higher irradiation dose led to the more MCAPP immobilized in three dimensional crosslinked structure of the EVA matrix which could jointly enhance the flame retardant and electrical insulation properties of the EVA composites. So, the EVA composites with 180 kGy irradiation dose exhibited better dimensional stability than the EVA composites with 120 kGy due to the higher crosslinking degree. Moreover, the higher irradiation dose lead to the more MCAPP immobilizated in crosslinked three-dimensional structure of EVA, enhancing the flame retardancy and electrical insulation properties of the EVA composites. After ageing test in hot water at 80 °C for 2 weeks, the EVA/TPU/MCAPP composite with 180 kGy could still maintain the UL-94 V-0 rating and the limiting oxygen index (LOI) value was as high as 30%. This investigation indicated the flame retardant EVA cable containing MCAPP could achieve stable properties and lower electrical fire hazard risk during long-term hot water ageing test.
A catalyst-free, temperature controlled gelation system for in-mold fabrication of microgels.
Krüger, Andreas J D; Köhler, Jens; Cichosz, Stefan; Rose, Jonas C; Gehlen, David B; Haraszti, Tamás; Möller, Martin; De Laporte, Laura
2018-06-19
Anisometric microgels are prepared via thermal crosslinking using an in-mold polymerization technique. Star-shaped poly(ethylene oxide-stat-propylene oxide) polymers, end-modified with amine and epoxy groups, form hydrogels, of which the mechanical properties and gelation rate can be adjusted by the temperature, duration of heating, and polymer concentration. Depending on the microgel stiffness, the rod-shaped microgels self-assemble into ordered or disordered structures.
Yin, Si; Zhang, Dangfeng; Du, Hui; Du, Heng; Yin, Zhanhai; Qiu, Yusheng
2015-01-01
Although many total hip bearing implants are widely used all over the world, simultaneous comparisons across the numerous available bearing surfaces are rare. The purpose of this study was to compare the survivorship of total hip arthroplasty (THA) with six available bearing implants. We conducted a systematic review of randomized controlled trials (RCTs) reporting survivorship or revision of ceramic-on-ceramic (CoC), ceramic-on-conventional polyethylene (CoPc), ceramic-on-highly-crosslinked polyethylene (CoPxl), metal-on-conventional polyethylene (MoPc), metal-on-highly-crosslinked polyethylene (MoPxl), or metal-on-metal (MoM) bearing implants. The synthesis of present evidence was performed by both the traditional direct-comparison meta-analysis and network meta-analysis. In total, 40 RCTs involving a total of 5321 THAs were identified. The pooled data of network meta-analysis showed no difference in relative risk (RR) of revision across CoC, CoPc, CoPxl and MoPxl bearings. However, the MoM bearing was demonstrated with a significant higher risk of revision compared with CoC (RR 5.10; 95% CI=1.62 to 16.81), CoPc (RR 4.80; 95% CI=1.29 to 17.09), or MoPxl (RR 3.85; 95% CI=1.16 to 14.29), and the MoPc bearing was indicated with a higher risk of revision compared with CoC (RR 2.83; 95% CI=1.20 to 6.63). The ranking probabilities of the effective interventions also revealed the inferiority of the MoM and MoPc implants in survivorship (both 0%, 95% CI=0% to 0%) compared with CoC (39%, 95% CI=0% to 100%), CoPc (33%, 95% CI=0% to 100%), CoPxl (7%, 95% CI=0% to 100%) or MoPxl (21%, 95% CI=0% to 100%). The present evidence indicated the similar performance in survivorship among CoC, CoPc, CoPxl and MoPxl bearing implants, and that all likely have superiority compared with the MoM and MoPc bearing implants in THA procedures. Long-term RCT data are required to confirm these conclusions and better inform clinical decisions.
In situ diselenide-crosslinked polymeric micelles for ROS-mediated anticancer drug delivery.
Deepagan, V G; Kwon, Seunglee; You, Dong Gil; Nguyen, Van Quy; Um, Wooram; Ko, Hyewon; Lee, Hansang; Jo, Dong-Gyu; Kang, Young Mo; Park, Jae Hyung
2016-10-01
Stimuli-responsive micelles have emerged as the drug carrier for cancer therapy since they can exclusively release the drug via their structural changes in response to the specific stimuli of the target site. Herein, we developed the in situ diselenide-crosslinked micelles (DCMs), which are responsive to the abnormal ROS levels of tumoral region, as anticancer drug carriers. The DCMs were spontaneously derived from selenol-bearing triblock copolymers consisting of polyethylene glycol (PEG) and polypeptide derivatives. During micelle formation, doxorubicine (DOX) was effectively encapsulated in the hydrophobic core, and diselenide crosslinks were formed in the shell. The DCMs maintained their structural integrity, at least for 6 days in physiological conditions, even in the presence of destabilizing agents. However, ROS-rich conditions triggered rapid release of DOX from the DOX-encapsulating DCMs (DOX-DCMs) because the hydrophobic diselenide bond was cleaved into hydrophilic selenic acid derivatives. Interestingly, after their systemic administration into the tumor-bearing mice, DOX-DCMs delivered significantly more drug to tumors (1.69-fold and 3.73-fold higher amount compared with their non-crosslinked counterparts and free drug, respectively) and effectively suppressed tumor growth. Overall, our data indicate that DCMs have great potential as drug carriers for anticancer therapy. Copyright © 2016 Elsevier Ltd. All rights reserved.
Tao, Yong; Tong, Xinming; Zhang, Yan; Lai, Jingjing; Huang, Yanbin; Jiang, Yan-Rong; Guo, Bao-Hua
2013-02-01
Currently there is no material that can be used as a long-term vitreous substitute, and this remains an unmet clinical need in ophthalmology. In this study, we developed an injectable, in situ chemically crosslinked hydrogel system and evaluated it in a rabbit model. The system consisted of two components, both based on multi-functional poly(ethylene glycol) (PEG) but with complementarily reactive end groups of thiol and active vinyl groups, respectively. The two components are mixed and injected as a solution mixture, react in vivo via the Michael addition route and form a chemically crosslinked hydrogel in situ. The linkages between the end groups and the backbone PEG chains are specially designed to ensure that the final network structure is hydrolysis-resistant. In the rabbit study and with an optimized operation protocol, we demonstrated that the hydrogel indeed formed in situ after injection, and remained transparent and stable during the study period of 9 months without significant adverse reactions. In addition, the hydrogel formed in situ showed rheological properties very similar to the natural vitreous. Therefore, our study demonstrated that this in situ chemically crosslinked PEG gel system is suitable as a potential long-term vitreous substitute. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.
Polymer Micelles with Cross-Linked Polyanion Core for Delivery of a Cationic Drug Doxorubicin
Kim, Jong Oh; Kabanov, Alexander V.; Bronich, Tatiana K.
2009-01-01
Polymer micelles with cross-linked ionic cores were prepared by using block ionomer complexes of poly(ethylene oxide)-b-poly(methacrylic acid) (PEO-b-PMA) copolymer and divalent metal cations as templates. Doxorubicin (DOX), an anthracycline anticancer drug, was successfully incorporated into the ionic cores of such micelles via electrostatic interactions. A substantial drug loading level (up to 50 w/w %) was achieved and it was strongly dependent on the structure of the cross-linked micelles and pH. The drug-loaded micelles were stable in aqueous dispersions exhibiting no aggregation or precipitation for a prolonged period of time. The DOX-loaded polymer micelles exhibited noticeable pH-sensitive behavior with accelerated release of DOX in acidic environment due to the protonation of carboxylic groups in the cores of the micelles. The attempt to protect the DOX-loaded core with the polycationic substances resulted in the decrease of loading efficacy and had a slight effect on the release characteristics of the micelles. The DOX-loaded polymer micelles exhibited a potent cytotoxicity against human A2780 ovarian carcinoma cells. These results point to a potential of novel polymer micelles with cross-linked ionic cores to be attractive carriers for the delivery of DOX. PMID:19386272
Yu, Shuangjiang; Ding, Jianxun; He, Chaoliang; Cao, Yue; Xu, Weiguo; Chen, Xuesi
2014-05-01
Nanoscale carriers that stably load drugs in blood circulation and release the payloads in desirable sites in response to a specific trigger are of great interest for smart drug delivery systems. For this purpose, a novel type of disulfide core cross-linked micelles, which are facilely fabricated by cross-linking of poly(ethylene glycol)/polyurethane block copolymers containing cyclic disulfide moieties via a thiol-disulfide exchange reaction, are developed. A broad-spectrum anti-cancer drug, doxorubicin (DOX), is loaded into the micelles as a model drug. The drug release from the core cross-linked polyurethane micelles (CCL-PUMs) loaded with DOX is suppressed in normal phosphate buffer saline (PBS), whereas it is markedly accelerated with addition of an intracellular reducing agent, glutathione (GSH). Notably, although DOX-loaded CCL-PUMs display lower cytotoxicity in vitro compared to either free DOX or DOX-loaded uncross-linked polyurethane micelles, the drug-loaded CCL-PUMs show the highest anti-tumor efficacy with reduced toxicity in vivo. Since enhanced anti-tumor efficacy and reduced toxic side effects are key aspects of efficient cancer therapy, the novel reduction-responsive CCL-PUMs may hold great potential as a bio-triggered drug delivery system for cancer therapy. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Singh, Mansi; Verma, Sanjeev K.; Biswas, Ipsita; Mehta, Rajeev
2018-05-01
The steady-shear viscosity and dynamic visco-elastic behavior of suspensions of 20 wt% fumed silica-polyethylene glycol (PEG200) shear thickening fluid (STF) with different concentrations of various molecular weight PEG (4600, 6000 and 10000) has been studied. The results demonstrate that with an increase in the molecular weight of dispersing medium, the shear thickening parameters are significantly enhanced. In steady-state rheology, addition of PEG6000 as an additive results in high shear thickening at both low and high temperatures whereas in dynamic state, PEG4600 gives high values of all dynamic parameters. Additionally, long polymer can interconnect several particles, acting as cross-links which explain the mechanism of the enhancement in viscosity. Interestingly, compositions having PEG10000 as additive exhibits shear thinning rheology. Long polymer chains increases hydrodynamic forces thus aggregation of particles increases. Also, the results demonstrate the effect of high molecular weight PEGs on the elasticity and stability of the STF, which is important with regard to high impact resisting applications.
Prai-In, Yingrak; Boonthip, Chatchai; Rutnakornpituk, Boonjira; Wichai, Uthai; Montembault, Véronique; Pascual, Sagrario; Fontaine, Laurent; Rutnakornpituk, Metha
2016-10-01
Surface modification of magnetic nanoparticle (MNP) with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) (PEO-b-PVDM) diblock copolymers and its application as recyclable magnetic nano-support for adsorption with antibody were reported herein. PEO-b-PVDM copolymers were first synthesized via a reversible addition-fragmentation chain-transfer (RAFT) polymerization using poly(ethylene oxide) chain-transfer agent as a macromolecular chain transfer agent to mediate the RAFT polymerization of VDM. They were then grafted on amino-functionalized MNP by coupling with some azlactone rings of the PVDM block to form magnetic nanoclusters with tunable cluster size. The nanocluster size could be tuned by adjusting the chain length of the PVDM block. The nanoclusters were successfully used as efficient and recyclable nano-supports for adsorption with anti-rabbit IgG antibody. They retained higher than 95% adsorption of the antibody during eight adsorption-separation-desorption cycles, indicating the potential feasibility in using this novel hybrid nanocluster as recyclable support in cell separation applications. Copyright © 2016 Elsevier B.V. All rights reserved.
Chen, Chih-Kuang; Lin, Wei-Jen; Hsia, Yu; Lo, Leu-Wei
2017-03-01
Well-defined poly(ethylene glycol)-b-allyl functional polylactide-b-polylactides (PEG-APLA-PLAs) are synthesized through sequential ring-opening polymerization. PEG-APLA-PLAs that have amphiphilic properties and reactive allyl side chains on their intermediate blocks are successfully transferred to core-shell interface cross-linked micelles (ICMs) by micellization and UV-initiated irradiation. ICMs have demonstrated enhanced colloidal stability in physiological-mimicking media. Hydrophobic molecules such as Nile Red or doxorubicin (Dox) are readily loaded into ICMs; the resulting drug-ICM formulations possess slow and sustained drug release profiles under physiological-mimicking conditions. ICMs exhibit negligible cytotoxicity in human uterine sarcoma cancer cells by using biodegradable aliphatic polyester as the hydrophobic segments. Relative to free Dox, Dox-loaded ICMs show a reduced cytotoxicity due to the late intracellular release of Dox from ICMs. Overall, ICMs represent a new type of biodegradable cross-linked micelle and can be employed as a promising platform for delivering a broad variety of hydrophobic drugs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Microenvironment-Sensitive Multimodal Contrast Agent for Prostate Cancer Diagnosis
2015-10-01
with a biopolymer (i.e. starch ) to improve biocompatibility, and tagged with prostate cancer-targeting ligands. A significant challenge to translation... starch coating of 50 nm and 100 nm SPIONs was crosslinked and coated with amine groups, and then functionalized with NHS-polyethylene glycol (PEG) of...varying molecular weight (i.e., 2k, 5k or 20k Da) as shown in Scheme 1. Scheme 1. Surface modification of starch -coated SPIONs into aminated and
Microenvironment Sensitive Multimodal Contrast Agent for Prostate Cancer Diagnosis
2016-10-01
coated with a biopolymer (i.e. starch ) to improve biocompatibility, and tagged with prostate cancer-targeting ligands. A significant challenge to...The starch coating of 50 nm and 100 nm SPIONs was crosslinked and coated with amine groups, and then functionalized with NHS-polyethylene glycol (PEG...of varying molecular weight (i.e., 2k, 5k or 20k Da) as shown in Scheme 1. Scheme 1. Surface modification of starch -coated SPIONs into aminated
Kim, Jinku; Yaszemski, Michael J.; Lu, Lichun
2010-01-01
Novel biodegradable injectable poly(ethylene glycol) (PEG) based macromers were synthesized by reacting low molecular weight PEG (MW: 200) and dicarboxylic acids such as sebacic acid or terephthalic acid. Chemical structures of the resulting polymers were confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy characterizations. Differential scanning calorimetry (DSC) showed that these polymers were completely amorphous above room temperature. After photopolymerization, dynamic elastic shear modulus of the crosslinked polymers was up to 1.5 MPa and compressive modulus was up to 2.2 MPa depending on the polymer composition. The in vitro degradation study showed that mass losses of these polymers were gradually decreased over 23 weeks of period in simulated body fluid. By incorporating up to 30 wt% of 2-hydroxyethyl methylmethacrylate (HEMA) into the crosslinking network, the dynamic elastic modulus and compressive modulus was significantly increased up to 7.2 MPa and 3.2 MPa, respectively. HEMA incorporation also accelerated degradation as indicated by significantly higher mass loss of up to 27% after 20 weeks of incubation. Cytocompatability studies using osteoblasts and neural cells revealed that cell metabolic activity on these polymers with or without HEMA was close to the control tissue culture polystyrene. The PEG based macromers developed in this study may be useful as scaffolds or cell carriers for tissue engineering applications. PMID:18655146
DOE Office of Scientific and Technical Information (OSTI.GOV)
Narasimhan, Diwahar; Collins, Gregory T.; Nance, Mark R.
No small-molecule therapeutic is available to treat cocaine addiction, but enzyme-based therapy to accelerate cocaine hydrolysis in serum has gained momentum. Bacterial cocaine esterase (CocE) is the fastest known native enzyme that hydrolyzes cocaine. However, its lability at 37 C has limited its therapeutic potential. Cross-linking subunits through disulfide bridging is commonly used to stabilize multimeric enzymes. Herein we use structural methods to guide the introduction of two cysteine residues within dimer interface of CocE to facilitate intermolecular disulfide bond formation. The disulfide-crosslinked enzyme displays improved thermostability, particularly when combined with previously described mutations that enhance stability (T172R-G173Q). The newlymore » modified enzyme yielded an extremely stable form of CocE (CCRQ-CocE) that retained greater than 90% of its activity after 41 days at 37 C, representing an improvement of more than 4700-fold over the wild-type enzyme. CCRQ-CocE could also be modified by polyethylene glycol (PEG) polymers, which improved its in vivo residence time from 24 to 72 h, as measured by a cocaine lethality assay, by self-administration in rodents, and by measurement of inhibition of cocaine-induced cardiovascular effects in rhesus monkeys. PEG-CCRQ elicited negligible immune response in rodents. Subunit stabilization and PEGylation has thus produced a potential protein therapeutic with markedly higher stability both in vitro and in vivo.« less
Narasimhan, Diwahar; Collins, Gregory T.; Nance, Mark R.; Nichols, Joseph; Edwald, Elin; Chan, Jimmy; Ko, Mei-Chuan; Woods, James H.; Tesmer, John J. G.
2011-01-01
No small-molecule therapeutic is available to treat cocaine addiction, but enzyme-based therapy to accelerate cocaine hydrolysis in serum has gained momentum. Bacterial cocaine esterase (CocE) is the fastest known native enzyme that hydrolyzes cocaine. However, its lability at 37°C has limited its therapeutic potential. Cross-linking subunits through disulfide bridging is commonly used to stabilize multimeric enzymes. Herein we use structural methods to guide the introduction of two cysteine residues within dimer interface of CocE to facilitate intermolecular disulfide bond formation. The disulfide-crosslinked enzyme displays improved thermostability, particularly when combined with previously described mutations that enhance stability (T172R-G173Q). The newly modified enzyme yielded an extremely stable form of CocE (CCRQ-CocE) that retained greater than 90% of its activity after 41 days at 37°C, representing an improvement of more than 4700-fold over the wild-type enzyme. CCRQ-CocE could also be modified by polyethylene glycol (PEG) polymers, which improved its in vivo residence time from 24 to 72 h, as measured by a cocaine lethality assay, by self-administration in rodents, and by measurement of inhibition of cocaine-induced cardiovascular effects in rhesus monkeys. PEG-CCRQ elicited negligible immune response in rodents. Subunit stabilization and PEGylation has thus produced a potential protein therapeutic with markedly higher stability both in vitro and in vivo. PMID:21890748
Son, Kuk Hui; Lee, Jin Woo
2016-10-20
The swelling properties and thermal transition of hydrogels can be tailored by changing the hydrophilic-hydrophobic balance of polymer networks. Especially, poly( N -isopropylacrylamide) (PNIPAm) has received attention as thermo-responsive hydrogels for tissue engineering because its hydrophobicity and swelling property are transited around body temperature (32 °C). In this study, we investigated the potential of poly(ethylene glycol) diacrylate (PEGDA) as a hydrophilic co-monomer and crosslinker of PNIPAm to enhance biological properties of PNIPAm hydrogels. The swelling ratios, lower critical solution temperature (LCST), and internal pore structure of the synthesized p(NIPAm- co -PEGDA) hydrogels could be varied with changes in the molecular weight of PEGDA and the co-monomer ratios (NIPAm to PEGDA). We found that increasing the molecular weight of PEGDA showed an increase of pore sizes and swelling ratios of the hydrogels. In contrast, increasing the weight ratio of PEGDA under the same molecular weight condition increased the crosslinking density and decreased the swelling ratios of the hydrogels. Further, to evaluate the potential of these hydrogels as cell sheets, we seeded bovine chondrocytes on the p(NIPAm- co -PEGDA) hydrogels and observed the proliferation of the seed cells and their detachment as a cell sheet upon a decrease in temperature. Based on our results, we confirmed that p(NIPAm- co -PEGDA) hydrogels could be utilized as cell sheets with enhanced cell proliferation performance.
Lund, Vidar; Anderson-Glenna, Mary; Skjevrak, Ingun; Steffensen, Inger-Lise
2011-09-01
The objectives of this study were to investigate migration of volatile organic compounds (VOCs) from cross-linked polyethylene (PEX) pipes used for drinking water produced by different production methods, and to evaluate their potential risk for human health and/or influence on aesthetic drinking water quality. The migration tests were carried out in accordance with EN-1420-1, and VOCs were analysed by gas chromatography-mass spectrometry. The levels of VOC migrating from new PEX pipes were generally low, and decreasing with time of pipe use. No association was found between production method of PEX pipes and concentration of migration products. 2,4-di-tert-butyl phenol and methyl tert-butyl ether (MTBE) were two of the major individual components detected. In three new PEX pipes, MTBE was detected in concentrations above the recommended US EPA taste and odour value for drinking water, but decreased below this value after 5 months in service. However, the threshold odour number (TON) values for two pipes were similar to new pipes even after 1 year in use. For seven chemicals for which conclusions on potential health risk could be drawn, this was considered of no or very low concern. However, odour from some of these pipes could negatively affect drinking water for up to 1 year.
Son, Dong-Ick; Park, Dong-Hee; Choi, Won Kook; Cho, Sung-Hwan; Kim, Won-Tae; Kim, Tae Whan
2009-05-13
The bistable effects of ZnO nanoparticles embedded in an insulating poly(methyl methacrylate) (PMMA) polymer single layer by using flexible polyethylene terephthalate (PET) substrates were investigated. Transmission electron microscopy (TEM) images revealed that ZnO nanoparticles were formed inside the PMMA polymer layer. Current-voltage (I-V) measurement on the Al/ZnO nanoparticles embedded in an insulating PMMA polymer layer/ITO/PET structures at 300 K showed a nonvolatile electrical bistability behavior with a flat-band voltage shift due to the existence of the ZnO nanoparticles, indicative of trapping, storing, and emission of charges in the electronic states of the ZnO nanoparticles. The carrier transport mechanism of the bistable behavior for the fabricated organic bistable device (OBD) structures is described on the basis of the I-V results by analyzing the effect of space charge.
Jalani, Ghulam; Jung, Chan Woo; Lee, Jae Sang; Lim, Dong Woo
2014-01-01
Stimuli-responsive, polymer-based nanostructures with anisotropic compartments are of great interest as advanced materials because they are capable of switching their shape via environmentally-triggered conformational changes, while maintaining discrete compartments. In this study, a new class of stimuli-responsive, anisotropic nanofiber scaffolds with physically and chemically distinct compartments was prepared via electrohydrodynamic cojetting with side-by-side needle geometry. These nanofibers have a thermally responsive, physically-crosslinked compartment, and a chemically-crosslinked compartment at the nanoscale. The thermally responsive compartment is composed of physically crosslinkable poly(N-isopropylacrylamide) poly(NIPAM) copolymers, and poly(NIPAM-co-stearyl acrylate) poly(NIPAM-co-SA), while the thermally-unresponsive compartment is composed of polyethylene glycol dimethacrylates. The two distinct compartments were physically crosslinked by the hydrophobic interaction of the stearyl chains of poly(NIPAM-co-SA) or chemically stabilized via ultraviolet irradiation, and were swollen in physiologically relevant buffers due to their hydrophilic polymer networks. Bicompartmental nanofibers with the physically-crosslinked network of the poly(NIPAM-co-SA) compartment showed a thermally-triggered shape change due to thermally-induced aggregation of poly(NIPAM-co-SA). Furthermore, when bovine serum albumin and dexamethasone phosphate were separately loaded into each compartment, the bicompartmental nanofibers with anisotropic actuation exhibited decoupled, controlled release profiles of both drugs in response to a temperature. A new class of multicompartmental nanofibers could be useful for advanced nanofiber scaffolds with two or more drugs released with different kinetics in response to environmental stimuli. PMID:24872702
[Determination of a Friction Coefficient for THA Bearing Couples].
Vrbka, M; Nečas, D; Bartošík, J; Hartl, M; Křupka, I; Galandáková, A; Gallo, J
2015-01-01
The wear of articular surfaces is considered one of the most important factors limiting the life of total hip arthroplasty (THA). It is assumed that the particles released from the surface of a softer material induce a complex inflammatory response, which will eventually result in osteolysis and aseptic loosening. Implant wear is related to a friction coefficient which depends on combination of the materials used, roughness of the articulating surfaces, internal clearance, and dimensions of the prosthesis. The selected parameters of the bearing couples tested were studied using an experimental device based on the principle of a pendulum. Bovine serum was used as a lubricant and the load corresponded to a human body mass of 75 kg. The friction coefficient was derived from a curve of slowdown of pendulum oscillations. Roughness was measured with a device working on the principle of interferometry. Clearance was assessed by measuring diameters of the acetabular and femoral heads with a 3D optical scanner. The specimens tested included unused metal-on-highly cross-linked polyethylene, ceramic-on-highly cross-linked polyethylene and ceramic-on-ceramic bearing couples with the diameters of 28 mm and 36 mm. For each measured parameter, an arithmetic mean was calculated from 10 measurements. 1) The roughness of polyethylene surfaces was higher by about one order of magnitude than the roughness of metal and ceramic components. The Protasul metal head had the least rough surface (0.003 μm). 2) The ceramic-on-ceramic couples had the lowest clearance. Bearing couples with polyethylene acetabular liners had markedly higher clearances ranging from 150 μm to 545 μm. A clearance increased with large femoral heads (up to 4-fold in one of the couple tested). 3) The friction coefficient was related to the combination of materials; it was lowest in ceramic-on-ceramic surfaces (0.11 to 0.12) and then in ceramic-on-polyethylene implants (0.13 to 0.14). The friction coefficient is supposed to increase with a decreasing femoral head diameter. However, in the bearing couples with polyethylene liners manufactured by one company, paradoxically, the friction coefficient slightly increased with an increase in femoral head size from 28 mm to 36 mm. 4) The lowest friction moment (< 3.5 Nm) was found for ceramic-on-ceramic implants 28 mm in diameter; the highest values were recorded in metal-on-polyethylene bearing couples 36 mm in diameter (> 7 Nm). Although our study confirmed that the bearing couples produced by different manufacturers varied to some extent in the parameters studied, in our opinion, this variability was not significant because it was not within an order of magnitude in any of the tests. The study showed that both the friction coefficient and the friction moment are affected more by the combination of materials than by the diameter of a femoral head. The best results were achieved in ceramic-on-ceramic implants.
Studies on crosslinked hydroxyapatite-polyethylene composite as a bone-analogue material
NASA Astrophysics Data System (ADS)
Smolko, E.; Romero, G.
2007-08-01
The paper examines the use of different types of polymeric matrix composites in hard-tissue replacement applications. The composite samples were prepared with hydroxyapatite (HA) powder and polyethylenes of different densities. The raw material was first compounded in the extruder and the resulting composite pre-forms were compression molded into desired plates and irradiated with different doses. Modulus of elasticity in tension, tensile strength, tensile fracture strain, elongation at break and gel content were obtained for all composites. Ceramic filler distribution was investigated under scanning electron microscopy (SEM). With HA incorporated in the samples an increase in the values of Young's Modulus, (stiffness) was observed, while elongation at break decreased with the amount of filler, showing increase of brittleness. Tensile strengths at yield and at break decreased with the filler content for LD and MDPE and stayed constant for HDPE.
Lu, Hailin; Ren, Shanshan; Li, Xing; Guo, Junde; Dong, Guangneng; Li, Jianhui; Gao, Li
2018-08-01
Body fluid is normally the only lubricant after joint replacement surgery, but wear problems have occurred because body fluid has poor lubrication ability. However, traditional lubricant would be diluted by body fluids and then absorbed by the human body. Therefore, an injectable gel with the ability to slow-release lubricant was designed to replace the joint capsule. The proposed gel, poly(ethylene glycol)/chitosan/sodium glycerophosphate (PEG/CS/GP) composite gel was then tested. The tribology results showed that the PEG/CS/GP gel had excellent slow-release properties, especially under pressure, and the PEG played an important role in improving the gel's rheological and mechanical properties. Moreover, this study revealed that the release solution had a good lubrication effect because the PEG and GP could crosslink via the hydrogen bond effect.
Nanoscale Assembly of Actuating Cilia-Mimetic
NASA Astrophysics Data System (ADS)
Baird, Lance; Breidenich, Jennifer; Land, Bruce; Hayes, Allen; Benkoski, Jason; Keng, Pei; Pyun, Jeffrey
2009-03-01
The cilium is among the smallest mechanical actuators found in nature. We have taken inspiration from this design to create magnetic nanochains, measuring approximately 1-5 μm long and 25 nm in diameter. Fabricated from the self-assembly of cobalt nanoparticles, these flexible filaments actuate in an oscillating magnetic field. The cobalt nanoparticles were functionalized with a polystyrene/benzaldehyde surface coating, thus allowing the particles to form imine bonds with one another in the presence of a diamine terminated polyethylene glycol. These imine bonds effectively cross-linked the particles and held the nanochains together in the absence of a magnetic field. Using design of experiments (DOE) to efficiently screen the effects of cobalt nanoparticle concentration, crosslinker concentration, and surface chemistry, we determined that the morphology of the final structures could be explained primarily by physical interactions (i.e. magnetic forces) rather than chemistry.
NASA Astrophysics Data System (ADS)
Daran-Daneau, Cyril
In order to answer the energetic needs of the future, insulation, which is the central piece of high voltage equipment, has to be reinvented. Nanodielectrics seem to be the promise of a mayor technological breakthrough. Based on nanocomposites with a linear low density polyethylene matrix reinforced by nano-clays and manufactured from a commercial master batch, the present thesis aims to characterise the accuracy of measurement techniques applied on nanodielectrics and also the dielectric properties of these materials. Thus, dielectric spectroscopy accuracy both in frequency and time domain is analysed with a specific emphasis on the impact of gold sputtering of the samples and on the measurements transposition from time domain to frequency domain. Also, when measuring dielectric strength, the significant role of surrounding medium and sample thickness on the variation of the alpha scale factor is shown and analysed in relation with the presence of surface partial discharges. Taking into account these limits and for different nanoparticles composition, complex permittivity as a function of frequency, linearity and conductivity as a function of applied electric field is studied with respect to the role that seems to play nanometrics interfaces. Similarly, dielectric strength variation as a function of nano-clays content is investigated with respect to the partial discharge resistance improvement that seems be induced by nanoparticle addition. Finally, an opening towards nanostructuration of underground cables' insulation is proposed considering on one hand the dielectric characterisation of polyethylene matrix reinforced by nano-clays or nano-silica nanodielectrics and on the other hand a succinct cost analysis. Keywords: nanodielectric, linear low density polyethylene, nanoclays, dielectric spectroscopy, dielectric breakdown
LONG TERM OPERATION ISSUES FOR ELECTRICAL CABLE SYSTEMS IN NUCLEAR POWER PLANTS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fifield, Dr Leonard S; Duckworth, Robert C; Glass III, Dr. Samuel W.
Nuclear power plants contain hundreds of kilometers of electrical cables including cables used for power, for instrumentation, and for control. It is essential that safety-related cable systems continue to perform following a design-basis event. Wholesale replacement of electrical cables in existing plants facing licensing period renewal is both impractical and cost-prohibitive. It is therefore important to understand the long term aging of cable materials to have confidence that aged cables will perform when needed. It is equally important in support of cable aging management to develop methods to evaluate the health of installed cables and inform selective cable replacement decisions.more » The most common insulation materials for electrical cables in nuclear power plants are cross-linked polyethylene and ethylene-propylene rubber. The mechanical properties of these materials degrade over time in the presence of environmental stresses including heat, gamma irradiation, and moisture. Mechanical degradation of cable insulation beyond a certain threshold is unacceptable because it can lead to insulation cracking, exposure of energized conductors, arcing and burning or loss of the ability of the cable system to function during a design-basis accident. While thermal-, radiation-, and moisture-related degradation of polymer insulation materials has been extensively studied over the last few decades, questions remain regarding the long-term performance of cable materials in nuclear plant-specific environments. Identified knowledge gaps include an understanding of the temperature-dependence of activation energies for thermal damage and an understanding of the synergistic effects of radiation and thermal stress on polymer degradation. Many of the outstanding questions in the aging behavior of cable materials relate to the necessity of predicting long-term field degradation using accelerated aging results from the laboratory. Materials degrade faster under more extreme conditions, but extension of behavior to long term degradation under more mild conditions, such as those experienced by most installed cables in nuclear power plants, is complicated by the fact that different degradation mechanisms may be involved in extreme and mild scenarios. The discrepancy in predicted results from short term, more extreme exposure and actual results from longer term, more mild exposures can be counter intuitive. For instance, due to the attenuation of oxidation penetration in material samples rapidly aged through exposure to high temperatures, the bulk of the samples may be artificially protected from thermal aging. In another example, simultaneous exposure of cable insulation material to heat and radiation may actually lead to less damage at higher temperatures than may be observed at lower temperatures. The Light Water Reactor Sustainability program of the United States (US) Department of Energy Office (DOE) of Nuclear Energy is funding research to increase the predictive understanding of electrical cable material aging and degradation in existing nuclear power plants in support of continued safe operation of plants beyond their initial license periods. This research includes the evaluation and development of methods to assess installed cable condition.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Qiao, B.; Teyssedre, G.; Laurent, C.
The mechanisms of electroluminescence from large band gap polymers used as insulation in electric components are still under debate. It becomes important to unravel the underlying physics of the emission because of increasing thermo-electric stress and a possible relationship between electroluminescence and field withstand. We report herein on the cathodoluminescence spectra of polyethylene and polypropylene films as a way to uncover the nature of its contributions to electroluminescence emission. It is shown that spectra from the two materials are structured around four elementary components, each of them being associated with a specific process contributing to the overall emission with differentmore » weights depending on excitation conditions and on materials. The cathodoluminescence and electroluminescence spectra of each material are reconstructed from the four spectral components and their relative contribution are discussed. It is shown that electroluminescence from polyethylene and polypropylene has the same origin pointing towards generic mechanisms in both.« less
Beaupre, Lauren A; Al-Houkail, Amro; Johnston, Donald William C
2016-06-01
Bearing surfaces in total hip arthroplasty (THA) may affect implant longevity and hence patient outcomes. This randomized clinical trial determined how ceramic-on-ceramic (CERAMIC) bearing THA affected joint-specific pain, function, and stiffness and prosthesis fixation/longevity over 10 postoperative years compared with ceramic-on-highly-crosslinked-polyethylene (POLYETHYLENE) bearing THA. This is a follow-up to previously reported 5-year outcomes. Subjects aged <61 years were randomized to CERAMIC (n = 48) or POLYETHYLENE (n = 44) THA. Subjects were assessed using the Western Ontario McMaster Osteoarthritis Index and the RAND 12-Item Health Survey preoperatively, and at 1, 5, and 10 years postoperatively. Plain radiographs were evaluated at 10 years for fixation, and medical records were reviewed for revisions. Of 92 subjects, 6 (7%) died within 10 years; 68 (79%) survivors provided radiographic and/or clinical follow-up at 10 years postoperatively. Improvements seen at 5 years in both the Western Ontario McMaster Osteoarthritis Index and RAND 12-Item Health Survey were retained at 10 years with no group differences (P > .48). There were no failures or loss of fixation related to bearing surfaces/wear in either group. Over 10 years, 3 subjects in the POLYETHYLENE group had revisions that were related to recurrent dislocation; 2 revisions were performed within 2 years of surgery, and one further subject underwent revision at 7 years postoperatively. This is one of the first randomized clinical trials to examine 10-year outcomes between CERAMIC and POLYETHYLENE bearing THAs. Both bearing surfaces performed well out to 10 years in subjects who were <61 years at time of surgery. Copyright © 2015 Elsevier Inc. All rights reserved.
Wear Measurement of Highly Cross-linked UHMWPE using a 7Be Tracer Implantation Technique
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wimmer, Markus A.; Laurent, Michael P.; Dwivedi, Yasha
2013-01-01
The very low wear rates achieved with the current highly cross-linked ultrahigh molecular weight polyethylenes (UHMWPE) used in joint prostheses have proven to be difficult to measure accurately by gravimetry. Tracer methods are there- fore being explored. The purpose of this study was to perform a proof-of-concept experiment on the use of the radioactive tracer beryllium-7 (7Be) for the determination of in vitro wear in a highly cross-linked orthopedic UHMWPE. Three cross-linked and four conventional UHMWPE pins made from compression- molded GUR 1050, were activated with 109 to 1010 7Be nuclei using a new implantation setup that produced a homogenousmore » distribution of implanted nuclei up to 8.5 lm below the surface. The pins were tested for wear in a six-station pin-on-flat appara- tus for up to 7.1 million cycles (178 km). A Germanium gamma detector was employed to determine activity loss of the UHMWPE pins at preset intervals during the wear test. The wear of the cross-linked UHMWPE pins was readily detected and esti- mated to be 17 6 3 lg per million cycles. The conventional-to- cross-linked ratio of the wear rates was 13.1 6 0.8, in the expected range for these materials. Oxidative degradation dam- age from implantation was negligible; however, a weak depend- ence of wear on implantation dose was observed limiting the number of radioactive tracer atoms that can be introduced. Future applications of this tracer technology may include the analysis of location-specific wear, such as loss of material in the post or backside of a tibial insert.« less
Eliezar, Jeaniffer; Scarano, Wei; Boase, Nathan R B; Thurecht, Kristofer J; Stenzel, Martina H
2015-02-09
The biodistribution of micelles with and without folic acid targeting ligands were studied using a block copolymer consisting of acrylic acid (AA) and polyethylene glycol methyl ether acrylate (PEGMEA) blocks. The polymers were prepared using RAFT polymerization in the presence of a folic acid functionalized RAFT agent. Oxoplatin was conjugated onto the acrylic acid block to form amphiphilic polymers which, when diluted in water, formed stable micelles. In order to probe the in vivo stability, a selection of micelles were cross-linked using 1,8-diamino octane. The sizes of the micelles used in this study range between 75 and 200 nm, with both spherical and worm-like conformation. The effects of cross-linking, folate conjugation and different conformation on the biodistribution were studied in female nude mice (BALB/c) following intravenous injection into the tail vein. Using optical imaging to monitor the fluorophore-labeled polymer, the in vivo biodistribution of the micelles was monitored over a 48 h time-course after which the organs were removed and evaluated ex vivo. These experiments showed that both cross-linking and conjugation with folic acid led to increased fluorescence intensities in the organs, especially in the liver and kidneys, while micelles that are not conjugated with folate and not cross-linked are cleared rapidly from the body. Higher accumulation in the spleen, liver, and kidneys was also observed for micelles with worm-like shapes compared to the spherical micelles. While the various factors of cross-linking, micelle shape, and conjugation with folic acid all contribute separately to prolong the circulation time of the micelle, optimization of these parameters for drug delivery devices could potentially overcome adverse effects such as liver and kidney toxicity.
Thermal conductivity and combustion properties of wheat gluten foams.
Blomfeldt, Thomas O J; Nilsson, Fritjof; Holgate, Tim; Xu, Jianxiao; Johansson, Eva; Hedenqvist, Mikael S
2012-03-01
Freeze-dried wheat gluten foams were evaluated with respect to their thermal and fire-retardant properties, which are important for insulation applications. The thermal properties were assessed by differential scanning calorimetry, the laser flash method and a hot plate method. The unplasticised foam showed a similar specific heat capacity, a lower thermal diffusivity and a slightly higher thermal conductivity than conventional rigid polystyrene and polyurethane insulation foams. Interestingly, the thermal conductivity was similar to that of closed cell polyethylene and glass-wool insulation materials. Cone calorimetry showed that, compared to a polyurethane foam, both unplasticised and glycerol-plasticised foams had a significantly longer time to ignition, a lower effective heat of combustion and a higher char content. Overall, the unplasticised foam showed better fire-proof properties than the plasticized foam. The UL 94 test revealed that the unplasticised foam did not drip (form droplets of low viscous material) and, although the burning times varied, self-extinguished after flame removal. To conclude both the insulation and fire-retardant properties were very promising for the wheat gluten foam. © 2012 American Chemical Society
Testing of flat conductor cable to Underwriters Laboratory standards UL719 and UL83
NASA Technical Reports Server (NTRS)
Loggins, R. W.; Herndon, R. H.
1974-01-01
The flat conductor cable (FCC) which was tested consisted of three AWG No. 12 flat copper conductors laminated between two films of polyethylene terephthalate (Mylar) insulation with a self-extinguishing polyester adhesive. Results of the tests conducted on this cable, according to specifications, warrants the use of this FCC for electrical interconnections in a surface nonmetallic protective covering.
Lifetime estimates for sterilizable silver-zinc battery separators
NASA Technical Reports Server (NTRS)
Cuddihy, E. F.; Walmsley, D. E.; Moacanin, J.
1972-01-01
The lifetime of separator membranes currently employed in the electrolyte environment of silver-zinc batteries was estimated at 3 to 5 years. The separator membranes are crosslinked polyethylene film containing grafted poly (potassium acrylate)(PKA), the latter being the hydrophilic agent which promotes electrolyte ion transport. The lifetime was estimated by monitoring the rate of loss of PKA from the separators, caused by chemical attack of the electrolyte, and relating this loss rate to a known relationship between battery performance and PKA concentration in the separators.
Methacrylate derivatives incorporating pyroglutamic acid.
Smith, Tara J; Mathias, Lon J
2002-01-01
Methacrylates containing pyroglutamic acid were synthesized in good yields. Methyl alpha-pyroglutamyl methylacrylate (PyMM) and methyl alpha-pyroglutamidoundecanoyl methylacrylate (PyUM) give very fast photopolymerization rates both in homopolymerizations and with widely used commercial monomers N-vinyl pyrrolidinone (NVP) and hydroxyethyl methacrylate (HEMA). Soluble or cross-linked homopolymers can be obtained depending upon polymerization temperature. Pyroglutamic methacrylates polymerize without added initiator in the melt. Solution cast, photocured, and thermally cured coatings gave good to excellent adhesion to poly(ethylene terephthalate) and glass surfaces.
Mechanically Strong, Polymer Cross-linked Aerogels (X-Aerogels)
NASA Technical Reports Server (NTRS)
Leventis, Nicholas
2006-01-01
Aerogels comprise a class of low-density, high porous solid objects consisting of dimensionally quasi-stable self-supported three-dimensional assemblies of nanoparticles. Aerogels are pursued because of properties above and beyond those of the individual nanoparticles, including low thermal conductivity, low dielectric constant and high acoustic impedance. Possible applications include thermal and vibration insulation, dielectrics for fast electronics, and hosting of functional guests for a wide variety of optical, chemical and electronic applications. Aerogels, however, are extremely fragile materials, hence they have found only limited application in some very specialized environments, for example as Cerenkov radiation detectors in certain types of nuclear reactors, aboard spacecraft as collectors of hypervelocity particles (refer to NASA's Stardust program) and as thermal insulators on planetary vehicles on Mars (refer to Sojourner Rover in 1997 and Spirit and Opportunity in 2004). Along these lines, the X-Aerogel is a new NASA-developed strong lightweight material that has resolved the fragility problem of traditional (native) aerogels. X-Aerogels are made by applying a conformal polymer coating on the surfaces of the skeletal nanoparticles of native aerogels (see Scanning Electron Micrographs). Since the relative amounts of the polymeric crosslinker and the backbone are comparable, X-Aerogels can be viewed either as aerogels modified by the templated accumulation of polymer on the skeletal nanoparticles, or as nanoporous polymers made by remplated casting of polymer on a nanostructured framework. The most striking feature of X-Aerogels is that for a nominal 3-fold increase in density (still a ultralighweight material), the mechanical strength can be up to 300 times higher than the strength of the underlying native aerogel. Thus, X-Aerogels combine a multiple of the specific compressive strength of steel, with the the thermal conductivity of styrofoam. X-Aerogels have been demonstrated with several polymers such as polyurethanes/polyureas, epoxies and polyolefins, while crosslinking of approximately 35 different oxide aerogels yields a range of dimensionally stable, porous lightweight materials with unique combinations of structural, magnetic and optical properties. The main theme in materials development for space exploration is multifunction. For example, use of one material for thermal insulation/structural component will free weight for useful payload. In that regard, X-aerogels are evaluated at NASA for cryogenic fuel storage tanks and for spacesuits. Along the same lines, major impact fro X-Aerogels is also expected in commercial applications for thermal/acoustic insulation, in catalytic reformers and converters, in filtration membranes and membranes for fuel cells, as platforms for optical, electrical and magnetic sensors, and as lightweight structural component for aircraft and satellites.
Manukumar, H M; Umesha, S
2017-12-01
In recent years much attention has been devoted to active packaging technologies that offer new opportunities for the food industry and food preservation. The spoilage of food products during post process handling leads to food contamination and causes life-threatening food-borne illness. The methicillin-resistant Staphylococcus aureus (MRSA) 090 is one of the food-borne pathogens associated with food poisoning that leads to an outbreak of perilous human infections worldwide. The development of resistance in bacteria and diffusion of coated synthetic preservatives into food are the major problem in food packaging industries. In the present work, we have developed a new food wrap method by cross-linking cinnamaldehyde on low-density polyethylene (Cin-C-LDPE) using novel photocrosslinker technology. The cinnamaldehyde showed potent antimicrobial activity (145mg/mL of MIC) against MRSA 090 and radical scavenging activity (RSA). The cinnamaldehyde was successfully cross-linked to LDPE and exhibited excellent antibiofilm properties against MRSA090 compared to bare LDPE. This positive interaction of developed Cin-C-LDPE against MRSA090 biofilm was confirmed by SEM and FT-IR studies, and results showed the damaged cell membrane architecture, inturn abridged adherence of MRSA090. The Cin-C-LDPE wrapped chicken, mutton, cheese, and grapes showed 2.5±0.15 log MRSA 090 reduction at the end of 10th day compared to the bare LDPE wrapped food samples. This clearly concludes that for the first time we have developed a novel Cin-C-LDPE food wrap technology effectively involved in biocidal activity against MRSA090. Applying this new strategy to develop food wrap containing nontoxic natural antimicrobial to target cell membrane components is the upcoming challenging and promising research gap remains in the food packaging industry for the future world. Copyright © 2017 Elsevier Ltd. All rights reserved.
Hall, Kristina K.; Gattás-Asfura, Kerim M.; Stabler, Cherie L.
2010-01-01
Functionalized alginate and PEG polymers were used to generate covalently linked alginate-PEG (XAlgPEG) microbeads of high stability. The cell-compatible Staudinger ligation scheme was used to chemoselectively cross-link phosphine-terminated poly(ethylene glycol) (PEG) to azide-functionalized alginate, resulting in XAlgPEG hydrogels. XAlgPEG microbeads were formed by co-incubation of the two polymers, followed by ionic cross-linking of the alginate using barium ions. The enhanced stability and gel properties of the resulting XAlgPEG microbeads, as well as the compatibility of these polymers for the encapsulation of islets and beta cells lines, were investigated. Our data show that XAlgPEG microbeads exhibit superior resistance to osmotic swelling compared to traditional barium cross-linked alginate (Ba-Alg) beads, with a 5-fold reduction in observed swelling, as well as resistance to dissolution via chelation solution. Diffusion and porosity studies found XAlgPEG beads to exhibit properties comparable to standard Ba-Alg. Our data found XAlgPEG microbeads to be highly cell compatible with insulinoma cell lines, as well as rat and human pancreatic islets, where the viability and functional assessment of cells within XAlgPEG were comparable to Ba-Alg controls. The remarkable improved stability, as well as demonstrated cellular compatibility, of XAlgPEG hydrogels makes them an appealing option for a wide variety of tissue engineering applications. PMID:20654745
NASA Astrophysics Data System (ADS)
Shen, Liguo; Li, Jianxi; Li, Renjie; Lin, Hongjun; Chen, Jianrong; Liao, Bao-Qiang
2018-04-01
In this study, a new strategy which blends low-density polyethylene (LDPE), magnesium hydroxide (MH) and lauryl acrylate by electron-beam radiation for production of LDPE-based composites with high performance was proposed. It was found that, MH played main roles in flame retardancy but reduced processing flow and mechanical properties of the composites. Meanwhile, melt flow rate (MFR) increased while viscosity of the composites decreased with lauryl acrylate content increased, facilitating LDPE composites processing. Electron beam radiation could prompt crosslinking of lauryl acrylate, which significantly enhanced the mechanical properties of LDPE composites. Meanwhile, lauryl acrylate addition only slightly decreased the flame retardancy, suggesting that LDPE composites could remain high flame retardancy even when lauryl acrylate content was high. The study highly demonstrated the feasibility to produce LDPE-based composites simultaneously with high flame retardancy and high mechanical properties by the blending strategy provided in this study.
Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Liu, Zhihong; Cui, Guanglei; Feng, Jiwen
2017-11-01
It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self-catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte (C-PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li + and considerable ionic conductivity of 8.9 × 10 -5 S cm -1 at ambient temperature. Moreover, the LiFePO 4 /C-PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self-catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes.
Incorporation of Active DNA/Cationic Polymer Polyplexes into Hydrogel Scaffolds
Lei, Yuguo; Huang, Suxian; Sharif-Kashani, Pooria; Chen, Yong; Kavehpour, Pirouz; Segura, Tatiana
2010-01-01
The effective and sustained delivery of DNA and siRNAs locally would increase the applicability of gene therapy in tissue regeneration and cancer therapy. One promising approach is to use hydrogel scaffolds to encapsulate and deliver nucleotides in the form of nanoparticles to the disease sites. However, this approach is currently limited by the inability to load concentrated and active gene delivery nanoparticles into the hydrogels due to the severe nanoparticle aggregation during the loading process. Here, we present a process to load concentrated and un-aggregated non-viral gene delivery nanoparticles, using DNA/polyethylene imine (PEI) polyplexes as an example, into neutral polyethylene glycol (PEG), negatively charged hyaluronic acid (HA) and protein fibrin hydrogels crosslinked through various chemistries. The encapsulated polyplexes are highly active both in vitro and in vivo. We believe this process will significantly advance the applications of hydrogel scaffold mediated non-viral gene delivery in tissue regeneration and cancer therapy. PMID:20822811
Akpalo, E; Bidault, L; Boissière, M; Vancaeyzeele, C; Fichet, O; Larreta-Garde, V
2011-06-01
Interpenetrating polymer network (IPN) architectures were conceived to improve the mechanical properties of a fibrin gel. Conditions allowing an enzymatic reaction to create one of the two networks in IPN architecture were included in the synthesis pathway. Two IPN series were carried out, starting from two polyethylene oxide (PEO) network precursors leading to different cross-linking densities of the PEO phase. The fibrin concentration varied from 5 to 20 wt.% in each series. The behavior of these materials during dehydration/hydration cycles was also studied. The mechanical properties of the resulting IPN were characterized in the wet and dry states. These self-supported biomaterials combine the properties of both a protein gel and a synthetic polymer. Finally, cells were grown on PEO/fibrin IPN, indicating that they are non-cytotoxic. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Tunable Enzymatic Activity and Enhanced Stability of Cellulase Immobilized in Biohybrid Nanogels.
Peng, Huan; Rübsam, Kristin; Jakob, Felix; Schwaneberg, Ulrich; Pich, Andrij
2016-11-14
This paper reports a facile approach for encapsulation of enzymes in nanogels. Our approach is based on the use of reactive copolymers able to get conjugated with enzyme and build 3D colloidal networks or biohybrid nanogels. In a systematic study, we address the following question: how the chemical structure of nanogel network influences the biocatalytic activity of entrapped enzyme? The developed method allows precise control of the enzyme activity and improvement of enzyme resistance against harsh store conditions, chaotropic agents, and organic solvents. The nanogels were constructed via direct chemical cross-linking of water-soluble reactive copolymers poly(N-vinylpyrrolidone-co-N-methacryloxysuccinimide) with proteins such as enhanced green fluorescent protein (EGFP) and cellulase in water-in-oil emulsion. The water-soluble reactive copolymers with controlled amount of reactive succinimide groups and narrow dispersity were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Poly(ethylene glycol) bis(3-aminopropyl) and branched polyethylenimine were utilized as model cross-linkers to optimize synthesis of nanogels with different architectures in the preliminary experiments. Biofluorescent nanogels with different loading amount of EGFP and varying cross-linking densities were obtained. We demonstrate that the biocatalytic activity of cellulase-conjugated nanogels (CNG) can be elegantly tuned by control of their cross-linking degrees. Circular dichroism (CD) spectra demonstrated that the secondary structures of the immobilized cellulase were changed in the aspect of α-helix contents. The secondary structures of cellulase in highly cross-linked nanogels were strongly altered compared with loosely cross-linked nanogels. The fluorescence resonance energy transfer (FRET) based study further revealed that nanogels with lower cross-linking degree enable higher substrate transport rate, providing easier access to the active site of the enzyme. The biohybrid nanogels demonstrated significantly improved stability in preserving enzymatic activity compared with free cellulase. The functional biohybrid nanogels with tunable enzymatic activity and improved stability are promising candidates for applications in biocatalysis, biomass conversion, or energy utilization fields.
Hou, Yaping; Schoener, Cody A.; Regan, Katherine R.; Munoz-Pinto, Dany; Hahn, Mariah S.; Grunlan, Melissa A.
2010-01-01
Inorganic-organic hydrogels with tunable chemical and physical properties were prepared from methacrylated star polydimethylsiloxane (PDMSstar-MA) and diacrylated poly(ethylene glycol) (PEG-DA) for use as tissue engineering scaffolds. Eighteen compositionally unique hydrogels were prepared by photo-crosslinking varying weight ratios of PEG-DA and PDMSstar-MA of different molecular weights (Mn): PEG-DA (Mn = 3.4k and 6k g/mol) and PDMSstar-MA (Mn = 1.8k, 5k and 7k g/mol). Introduction of PDMSstar-MA caused formation of discrete PDMS-enriched microparticles dispersed within the PEG matrix. The swelling ratio, mechanical properties in tension and compression, non-specific protein adhesion, controlled introduction of bioactivity and cytotoxicity of hydrogels were studied. This library of inorganic-organic hydrogels with tunable properties provides a useful platform to study the effect of scaffold properties on cell behavior. PMID:20146518
Freestanding, heat resistant microporous film for use in energy storage devices
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pekala, Richard W.; Cherukupalli, Srinivas; Waterhouse, Robert R.
Preferred embodiments of a freestanding, heat resistant microporous polymer film (10) constructed for use in an energy storage device (70, 100) implements one or more of the following approaches to exhibit excellent high temperature mechanical and dimensional stability: incorporation into a porous polyolefin film of sufficiently high loading levels of inorganic or ceramic filler material (16) to maintain porosity (18) and achieve low thermal shrinkage; use of crosslinkable polyethylene to contribute to crosslinking the polymer matrix (14) in a highly inorganic material-filled polyolefin film; and heat treating or annealing of biaxially oriented, highly inorganic material-filled polyolefin film above the meltingmore » point temperature of the polymer matrix to reduce residual stress while maintaining high porosity. The freestanding, heat resistant microporous polymer film embodiments exhibit extremely low resistance, as evidenced by MacMullin numbers of less than 4.5.« less
Self-repairable polyurethane networks by atmospheric carbon dioxide and water.
Yang, Ying; Urban, Marek W
2014-11-03
Sugar moieties were incorporated into cross-linked polyurethane (PUR) networks in an effort to achieve self-repairing in the presence of atmospheric carbon dioxide (CO2) and water (H2O). When methyl-α-D-glucopyranoside (MGP) molecules are reacted with hexamethylene diisocyanate trimer (HDI) and polyethylene glycol (PEG) to form cross-linked MGP-polyurethane (PUR) networks, these materials are capable of self-repairing in air. This process requires atmospheric amounts of CO2 and H2O, thus resembling plant behavior of carbon fixation during the photosynthesis cycle. Molecular processes responsible for this unique self-repair process involve physical diffusion of cleaved network segments as well as the formation of carbonate and urethane linkages. Unlike plants, MGP-PUR networks require no photo-initiated reactions, and they are thus capable of repair in darkness under atmospheric conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers
NASA Technical Reports Server (NTRS)
Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.
2007-01-01
Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.
Wannomae, Keith K; Christensen, Steven D; Freiberg, Andrew A; Bhattacharyya, Shayan; Harris, William H; Muratoglu, Orhun Kamil
2006-03-01
Irradiation decreases the wear of ultra-high molecular weight polyethylene (UHMWPE) but generates residual free radicals, precursors to long-term oxidation. Melting or annealing is used in quenching free radicals. We hypothesized that irradiated and once-annealed UHMWPE would oxidize while irradiated and melted UHMWPE would not, and that the oxidation in the former would increase wear. Acetabular liners were real-time aged by immersion in an aqueous environment that closely mimicked the temperature and oxygen concentration of synovial fluid. After 95 weeks of real-time aging, once-annealed components were oxidized; the melted components were not. The wear rate of the real-time aged irradiated and once-annealed components was higher than the literature reported values of other contemporary highly cross-linked UHMWPEs. Single annealing after irradiation used with terminal gamma sterilization may adversely affect the long-term oxidative stability of UHMWPE components.
Stabilization of penicillinase-hapten conjugate for enzyme immunoassay.
Omidfar, K; Rasaee, Mohammad J; Zaraee, Ali B; Amir, M Pour; Rahbarizadeh, F
2002-01-01
The influence of various additives, such as organic solvents, polyhydric alcohols, salts, polymers, and cross-linker, on the stability and storage ability of penicillinase-morphine conjugate was studied in liquid and solid (freeze dried) states. The results of these experiments showed that using low concentrations of CaCl2 (0.1-0.2%) could stabilize enzyme activity in both states for more than seven months. The immunoreactivity of antigen toward the antibody did not change significantly. However, a cross-linker such as glutaraldehyde and various additives such as dimethylsulfoxide, glycerol, polyethylene glycol, gelatin, dextran, ammonium sulfate, lactose, and sucrose did not have any effect on stability. In addition, it was found that the presence of lactose and sucrose in the lyophilization procedure gives a significant amount of protection to the enzyme, which could last for a period of seven months and preserve almost 95% of the enzyme activity, as well as immunoreactivity of the tracer molecule.
Wear Measurement of Highly Cross-Linked UHMWPE Using a 7Be Tracer Implantation Technique
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wimmer, Markus; Laurent, Michael P.; Dwivedi, Yash
2013-01-29
The very low wear rates achieved with the current highly cross-linked ultra-high molecular weight polyethylenes (UHMWPE) used in joint prostheses have proven to be difficult to measure accurately by gravimetry. Tracer methods are therefore being explored. The purpose of this study was to effect a proof-of-concept on the use of the radioactive tracer beryllium-7 (7Be) for the determination of wear in a highly cross-linked orthopedic UHMWPE. Three crosslinked and four conventional UHMWPE pins made from compression-molded GUR 1050, were activated with 109 to 1010 7Be nuclei using a new implantation setup that produced a homogenous distribution of implanted nuclei upmore » to 8.5 μm below the surface. The pins were tested for wear in a six-station pin-on-flat apparatus for up to 7.1 million cycles (178 km). A Germanium gamma detector was employed to determine activity loss of the UHMWPE pins at preset intervals during the wear test. The wear of the cross-linked UHMWPE pins was readily detected and estimated to be 17 ± 3 μg/Mc. The conventional-to-cross-linked ratio of the wear rates was 13.1 ± 0.8, in the expected range for these materials. It was estimated that implantation reduced the average wear rate by approximately 20%, and the oxidative degradation damage from implantation was negligible. Future applications of this tracer technology may include the analysis of location-specific wear, such as loss of material in the post or backside of a tibial insert.« less
Kyomoto, Masayuki; Moro, Toru; Takatori, Yoshio; Tanaka, Sakae; Ishihara, Kazuhiko
2015-03-01
Modifying the surface and substrate of a crosslinked polyethylene (CLPE) liner may be beneficial for high wear resistance as well as high oxidative stability and excellent mechanical properties, which would be useful in contributing to the long-term performance of orthopaedic bearings. A grafted poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer on a vitamin E-blended crosslinked PE (HD-CLPE[VE]) surface may provide hydrophilicity and lubricity without compromising the oxidative stability or mechanical properties. (1) Will the modifications (PMPC grafting and vitamin E blending) affect the lubrication characteristics of the CLPE surface? (2) Will the modifications affect wear resistance? (3) Will the modifications affect fatigue resistance? We investigated the effects of surface and substrate modifications (PMPC grafting and vitamin E blending) on the wear and fatigue fracture of thin CLPE samples. For each of the untreated and PMPC-grafted CLPE surfaces with and without vitamin E blended (four groups), wettability and lubricity surface analyses were conducted as well as multidirectional wear and impact-to-wear tests using a pin-on-disk testing machine. The water wettability and lubricity (CLPE [mean ± 95% confidence interval]: 23.2° ± 1.8°, 0.005 ± 0.001; HD-CLPE[VE]: 26.0° ± 2.3°, 0.009 ± 0.003) of the PMPC-grafted surfaces were greater (p < 0.001) than that (CLPE: 90.3° ± 1.2°, 0.067 ± 0.015; HD-CLPE[VE]: 90.8° ± 2.0°, 0.063 ± 0.008) of the untreated surface regardless of vitamin E additives. It was observed that the PMPC grafting (CLPE: 0.23 ± 0.06 mg; HD-CLPE[VE]: 0.05 ± 0.10 mg) was associated with reduced gravimetric wear (CLPE: 0.53 ± 0.08 mg, p = 0.004 HD-CLPE[VE]: 0.23 ± 0.07 mg, p = 0.038) in the multidirectional wear test. The PMPC-grafted surface characteristics did not appear to affect the impact fatigue resistance regardless of vitamin E blending. PMPC grafting improved the surface hydrophilicity and lubricity, and it reduced the gravimetric wear in terms of multidirectional sliding. It did not result in differences in terms of the impact-to-unidirectional sliding regardless of vitamin E blending. Further research is needed to evaluate the wear resistance of PMPC-grafted HD-CLPE(VE) in long-term hip simulator tests under normal and severe conditions, which may offer useful clues to the possible performance of these materials in vivo. Our preliminary in vitro findings suggest that some improvement in the wear performance of crosslinked polyethylene acetabular liners in total hip arthroplasty could be obtained using PMPC grafting. Further research is needed to evaluate the wear resistance of PMPC-grafted HD-CLPE(VE) in long-term hip simulator tests under normal and severe conditions, which may offer useful clues to the possible performance of these materials in vivo.
NASA Technical Reports Server (NTRS)
Miller, C. G.; Stephens, J. B. (Inventor)
1978-01-01
Shallow pools of liquid to collect low-temperature solar generated thermal energy are described. Narrow elongated trenches, grouped together over a wide area, are lined with a heat-absorbing black liner. The heat-absorbing liquid is kept separate from the thermal energy removing fluid by means such as clear polyethylene material. The covering for the pond may be a fluid or solid. If the covering is a fluid, fire fighting foam, continuously generated, or siloons are used to keep the surface covering clean and insulated. If the thermal energy removing fluid is a gas, a fluid insulation layer contained in a flat polyethlene tubing is used to cover the pond. The side of the tube directed towards the sun is treated to block out ultraviolet radiation and trap in infrared radiation.
1987-12-01
triphasic composite. Addition of the third filler yielded two effects. First, the filler provided sufficient mechanical stabilization of the composite...2000C. The stabilization was accomplished without diminishing the magnitude of the PTC effect. The triphasic composites also displayed equivalent or...differences in conductor and insulator --.-+icle size lead to the formation of quasi-compo- -s, resulting in a 3(0-3)-0 connectivity. Triphasic composites
Meng, Jia; Zhang, Yewen; Holé, Stéphane; Zheng, Feihu; An, Zhenlian
2018-04-12
Space charge migration characteristics play an important role in the evaluation of polymer insulation performance. However, an accurate description of charge carrier mobility in several typical insulating polymers such as polyethylene, polypropylene is currently not available. Recently, with the observation of a series of negative charge packet movements associated with the negative differential resistance characteristic of charge mobility in LDPE films, the extraction of charge mobility from the apparent charge packet movement has been attempted using appropriate methods. Based on the previous report of the successful derivation of charge mobility from experimental results using numerical methods, the present research improves the derivation accuracy and describes the details of the charge mobility derivation procedure. Back simulation results under several typical polarizing fields using the derived charge mobility are exhibited. The results indicate that both the NDR theory and the simulation models for the polyethylene materials are reasonable. A significant migration velocity difference between the charge carrier and the charge packet is observed. Back simulations of the charge packet under several typical polarizing fields using the obtained E-v curve show good agreement with the experimental results. The charge packet shapes during the migrations were also found to vary with the polarizing field.
Improvements to the Synthesis of Polyimide Aerogels
NASA Technical Reports Server (NTRS)
Meador, Mary Ann B.; Nguyen, Baochau N.; Guo, Haiquan; Vivod, Stephanie; He, Zuhui; Malow, Ericka; Silva, Rebecca
2011-01-01
Cross-linked polyimide aerogels are viable approach to higher temperature, flexible insulation for inflatable decelerators. Results indicate that the all-polyimide aerogels are as strong or stronger than polymer reinforced silica aerogels at the same density. Currently, examining use of carbon nanofiber and clay nanoparticles to improve performance. Flexible, polyimide aerogels have potential utility in other applications such as space suits, habitats, shelter applications, etc. where low dusting is desired
Modification of insulating diamond-like films by pulsed UV laser emission
NASA Astrophysics Data System (ADS)
Ageev, V. P.; Glushko, T. N.; Dorfman, V. F.; Kuzmichev, A. V.; Pypkin, B. N.
1991-07-01
The basic regimes of the modification of diamond-like a-C/Si/O:H films by the emission of the KrF laser are investigated. In particular, attention is given to the effect of the graphitization process on the spatial resolution of the dimensional treament. The possibility of the submicron cross-linking of the films using the methods of ablative UV laser lithography is demonstrated.
Chen, Wan Juan; Zeng, Xingrong; Lai, Xuejun; Li, Hongqiang; Fang, Wei Zhen; Hou, Fei
2016-08-17
How to effectively improve the tracking and erosion resistance of silicone rubber (SR) was an urgent topic in the field of high-voltage insulation. In this work, the tracking and erosion resistance of SR was significantly improved by incorporating platinum (Pt) catalyst and nitrogen-containing silane (NS). The suppression effect and mechanism of Pt/NS on tracking and erosion were studied by inclined plane (IP) test, thermogravimetry (TG), thermogravimetry-Fourier transform infrared spectrometry, laser Raman spectroscopy, and scanning electron microscopy. It revealed that when 1.4 phr of NS and 6.7 ppm of Pt were added, the tracking resistance of SR was improved from 2.5 to 4.5 kV level in the IP test, and the eroded mass was significantly reduced. This might be attributed to the synergistic effect of Pt/NS on silicone chains. At a high temperature produced by arc discharge, Pt/NS would catalyze radical cross-linking, meanwhile suppressing oxidation and depolymerization of silicone chains. Hence, a tightly cross-linked network was formed and protected inner materials from arc ablation. Moreover, carbon deposit during pyrolysis was suppressed by Pt/NS, which served as the secondary mechanism of tracking suppression.
Influence of γ-irradiation and temperature on the mechanical properties of EPDM cable insulation
NASA Astrophysics Data System (ADS)
Šarac, T.; Quiévy, N.; Gusarov, A.; Konstantinović, M. J.
2016-08-01
The mechanical properties of EPDM polymers, degraded as a result of extensive thermal and radiochemical aging treatment, are studied. The focus is given to dose rate effects in polymer insulation materials extracted from industrial cables in use in Belgian nuclear power plants. All studied mechanical characteristics such as the ultimate tensile stress, the Young's modulus, and the total elongation (or elongation at break) are found to be strongly affected by the irradiation dose. The ultimate tensile stress and Young's modulus are clearly exhibiting the dose rate effect, which originated from oxidation mediated interplay of polymer cross-linking and chain scission processes. The change of crossover between these two processes is found to be gradual, without critical dose rate or temperature values. On the contrary, the total elongation is observed not to be sensitive neither to irradiation temperature nor to the dose rate. Both cross-linking and chain scission seem to affect the total elongation in a similar way by reducing the average polymers chain length. This idea is confirmed by the model which shows that all total elongation data as a function of irradiation time can be reproduced by varying a single parameter, the pre-exponential factor of the irradiation rate constant.
Gao, B; Li, X J; Lin, M; Li, Y Y; Dong, Y
2018-02-09
Objective: To evaluate the application effect of nanofiber chitosan-collagen membrane (NCM) on guided bone regeneration (GBR). Methods: The mixture of collagen, chitosan, polyethylene oxide was used to make up the NCM by electrospinning, then the NCM was crosslinked by glutaraldehyde vapor. The physical property of the NCM was measured by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). MC3T3-E1 osteoblasts were cultured on NCM to characterize the biocompatibility. The effectiveness of four groups [contrast group, Bio-gide membrane (BGM), compressed chitosan-collagen menbrane (CCM), NCM/CCM] on bone regeneration were evaluated in critical-sized defects (diameter = 5 mm) in SD rats. Results: When the mixed solution consists of 4.0% collagen, 1.0% chitosan and 3.5% polyethylene oxide, the NCM could be validly fabricated by electrospinning. After cross-linking by glutaraldehyde vapor, the tensile strength and the stability of NCM in damp was enhanced. No cytotoxicity of the NCM was detected on MC3T3-E1 osteoblasts. In vivo study showed that the new bone regeneration ratio of NCM/CCM group was [(43.10±1.49)%], and this was similar to that of the group of BGM [(41.36±2.60)%] ( P> 0.05), but higher than that of the CCM group [(33.10±1.41)%] and the contrast group [(7.22±2.46)%] ( P< 0.05). Conclusions: The NCM can promote new bone regeneration effectively in GBR procedure.
Kondiah, Pierre P D; Tomar, Lomas K; Tyagi, Charu; Choonara, Yahya E; Modi, Girish; du Toit, Lisa C; Kumar, Pradeep; Pillay, Viness
2013-11-18
pH-sensitive microparticles were prepared using trimethyl-chitosan (TMC), poly(ethylene glycol)dimethacrylate (PEGDMA) and methacrylic acid (MAA) by free radical suspension polymerization, for the oral delivery of interferon-β (INF-β). The microparticles were subsequently compressed into a suitable oral tablet formulation. A Box-Behnken experimental design was employed for generating a series of formulations with varying concentrations of TMC (0.05-0.5 g/100 mL) and percentage crosslinker (polyethylene glycol diacrylate) (3-8%, w/w of monomers), for establishment of an optimized TMC-PEGDMA-MAA copolymeric microparticles. For pragmatism, insulin was initially employed as the model peptide for undertaking the preliminary experimentation and the optimized formulation was subsequently evaluated using INF-β. The prepared copolymeric microparticulate system was characterized for its morphological, porositometric and mucoadhesive properties. The optimized microparticles with 0.5 g/100 mL TMC and 3% crosslinker had an INF-β loading efficiency of 53.25%. The in vitro release of INF-β was recorded at 74% and 3% in intestinal (pH 6.8) and gastric (pH 1.2) pH from the oral tablet formulation, respectively. The tablet was further evaluated for plasma concentration of INF-β in the New Zealand White rabbit, and compared to a known subcutaneous formulation. The system showed an astounding effective release profile over 24h with higher INF-β plasma concentrations compared with the subcutaneous injection formulation. Copyright © 2013 Elsevier B.V. All rights reserved.
Weaver, Jessica D; Headen, Devon M; Hunckler, Michael D; Coronel, Maria M; Stabler, Cherie L; García, Andrés J
2018-07-01
The use of immunoisolating macrodevices in islet transplantation confers the benefit of safety and translatability by containing transplanted cells within a single retrievable device. To date, there has been limited development and characterization of synthetic poly(ethylene glycol) (PEG)-based hydrogel macrodevices for islet encapsulation and transplantation. Herein, we describe a two-component synthetic PEG hydrogel macrodevice system, designed for islet delivery to an extrahepatic islet transplant site, consisting of a hydrogel core cross-linked with a non-degradable PEG dithiol and a vasculogenic outer layer cross-linked with a proteolytically sensitive peptide to promote degradation and enhance localized vascularization. Synthetic PEG macrodevices exhibited equivalent passive molecular transport to traditional microencapsulation materials (e.g., alginate) and long-term stability in the presence of proteases in vitro and in vivo, out to 14 weeks in rats. Encapsulated islets demonstrated high viability within the device in vitro and the incorporation of RGD adhesive peptides within the islet encapsulating PEG hydrogel improved insulin responsiveness to a glucose challenge. In vivo, the implementation of a vasculogenic, degradable hydrogel layer at the outer interface of the macrodevice enhanced vascular density within the rat omentum transplant site, resulting in improved encapsulated islet viability in a syngeneic diabetic rat model. These results highlight the benefits of the facile PEG platform to provide controlled presentation of islet-supportive ligands, as well as degradable interfaces for the promotion of engraftment and overall graft efficacy. Copyright © 2018 Elsevier Ltd. All rights reserved.
McAvoy, Kathryn; Jones, David; Thakur, Raghu Raj Singh
2018-01-16
To investigate the sustained ocular delivery of small and large drug molecules from photocrosslinked poly(ethylene glycol) diacrylate (PEGDA) implants with varying pore forming agents. Triamcinolone acetonide and ovalbumin loaded photocrosslinked PEGDA implants, with or without pore-forming agents, were fabricated and characterised for chemical, mechanical, swelling, network parameters, as well as drug release and biocompatibility. HPLC-based analytical methods were employed for analysis of two molecules; ELISA was used to demonstrate bioactivity of ovalbumin. Regardless of PEGDA molecular weight or pore former composition all implants loaded with triamcinolone acetonide released significantly faster than those loaded with ovalbumin. Higher molecular weight PEGDA systems (700 Da) resulted in faster drug release of triamcinolone acetonide than their 250 Da counterpart. All ovalbumin released over the 56-day time period was found to be bioactive. Increasing PEGDA molecular weight resulted in increased system swelling, decreased crosslink density (Ve), increased polymer-water interaction parameter (χ), increased average molecular weight between crosslinks (Mc) and increased mesh size (ε). SEM studies showed the porosity of implants increased with increasing PEGDA molecular weight. Biocompatibility showed both PEGDA molecular weight implants were non-toxic when exposed to retinal epithelial cells over a 7-day period. Photocrosslinked PEGDA implant based systems are capable of controlled drug release of both small and large drug molecules through adaptations in the polymer system network. We are currently continuing evaluation of these systems as potential sustained drug delivery devices.
Yamamoto, Y; Sefton, M V
1998-01-01
Poly(ethylene glycol) (PEG) was grafted onto poly(acrylamide-co-vinyl amine) (poly(AM-co-VA)) film using tresylated PEG (TPEG) at 37 degrees C in aqueous buffers (pH 7.4) with a view to surface-modifying microencapsulated mammalian cells. Poly(AM-co-VA) film was synthesized by Hofmann degradation of a cross-linked poly(acrylamide) film. Conversion to vinyl amine on the surface of the film was approximately 50%, but bulk conversion was not observed; surface specificity was thought to be the result of cleavage of aminated polymer chains at the surface due to chain scission. Reaction between primary amine and TPEG gave a graft yield of 2 mol% (based on XPS) with respect to available surface amine groups, equivalent to 54 mol% ethylene oxide based on monomer units. Physical adsorption of non-activated polymer was done under identical conditions as a control and the difference in oxygen content was significant compared to TPEG. The type of buffer agent and buffer concentration did not influence graft yields. This graft reaction, which was completed in as little as 2 h was considered to be mild enough to be used for a surface modification of microcapsules containing cells without affecting their viability. Such a surface modification technique may prove to be a useful means of enhancing the biocompatibility of microcapsules (or any tissue engineering construct) even after cell encapsulation or seeding.
NASA Astrophysics Data System (ADS)
Sherazi, Tauqir A.; Rehman, Tayyiba; Naqvi, Syed Ali Raza; Shaikh, Ahson Jabbar; Shahzad, Sohail Anjum; Abbas, Ghazanfar; Raza, Rizwan; Waseem, Amir
2015-12-01
The surface of ultra-high molecular weight polyethylene (UHMWPE) powder was functionalized with styrene using chemical grafting technique. The grafting process was initiated through radical generation on base polymer matrix in the solid state by sodium thiosulfate, while peroxides formed at radical sites during this process were dissociated by ceric ammonium nitrate. Various factors were optimized and reasonably high level of monomer grafting was achieved, i.e., 15.6%. The effect of different acids as additive and divinyl benzene (DVB) as a cross-linking agent was also studied. Post-grafting sulfonation was conducted to introduce the ionic moieties to the grafted polymer. Ion-exchange capacity (IEC) was measured experimentally and is found to be 1.04 meq g-1, which is in close agreement with the theoretical IEC values. The chemical structure of grafted and functionalized polymer was characterized by attenuated total reflection infrared spectroscopy (ATR-FTIR) and thermal properties were investigated by thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC). Thermal analysis depicts that the presence of radicals on the polymer chain accelerates the thermal decomposition process. The results signify that the chemical grafting is an effective tool for substantial surface modification and subsequent functionalization of polyethylene.
Yoo, Youngmin; Kim, Byung Gon; Pak, Kwanyong; Han, Sung Jae; Song, Heon-Sik; Choi, Jang Wook; Im, Sung Gap
2015-08-26
We report an initiated chemical vapor deposition (iCVD) process to coat polyethylene (PE) separators in Li-ion batteries with a highly cross-linked, mechanically strong polymer, namely, polyhexavinyldisiloxane (pHVDS). The highly cross-linked but ultrathin pHVDS films can only be obtained by a vapor-phase process, because the pHVDS is insoluble in most solvents and thus infeasible with conventional solution-based methods. Moreover, even after the pHVDS coating, the initial porous structure of the separator is well preserved owing to the conformal vapor-phase deposition. The coating thickness is delicately controlled by deposition time to the level that the pore size decreases to below 7% compared to the original dimension. The pHVDS-coated PE shows substantially improved thermal stability and electrolyte wettability. After incubation at 140 °C for 30 min, the pHVDS-coated PE causes only a 12% areal shrinkage (versus 90% of the pristine separator). The superior wettability results in increased electrolyte uptake and ionic conductivity, leading to significantly improved rate performance. The current approach is applicable to a wide range of porous polymeric separators that suffer from thermal shrinkage and poor electrolyte wetting.
Tough stimuli-responsive supramolecular hydrogels with hydrogen-bonding network junctions.
Guo, Mingyu; Pitet, Louis M; Wyss, Hans M; Vos, Matthijn; Dankers, Patricia Y W; Meijer, E W
2014-05-14
Hydrogels were prepared with physical cross-links comprising 2-ureido-4[1H]-pyrimidinone (UPy) hydrogen-bonding units within the backbone of segmented amphiphilic macromolecules having hydrophilic poly(ethylene glycol) (PEG). The bulk materials adopt nanoscopic physical cross-links composed of UPy-UPy dimers embedded in segregated hydrophobic domains dispersed within the PEG matrix as comfirmed by cryo-electron microscopy. The amphiphilic network was swollen with high weight fractions of water (w(H2O) ≈ 0.8) owing to the high PEG weight fraction within the pristine polymers (w(PEG) ≈ 0.9). Two different PEG chain lengths were investigated and illustrate the corresponding consequences of cross-link density on mechanical properties. The resulting hydrogels exhibited high strength and resilience upon deformation, consistent with a microphase separated network, in which the UPy-UPy interactions were adequately shielded within hydrophobic nanoscale pockets that maintain the network despite extensive water content. The cumulative result is a series of tough hydrogels with tunable mechanical properties and tractable synthetic preparation and processing. Furthermore, the melting transition of PEG in the dry polymer was shown to be an effective stimulus for shape memory behavior.
Can green solvents be alternatives for thermal stabilization of collagen?
Mehta, Ami; Rao, J Raghava; Fathima, Nishter Nishad
2014-08-01
"Go Green" campaign is gaining light for various industrial applications where water consumption needs to be reduced. To resolve this, industries have adopted usage of green, organic solvents, as an alternative to water. For leather making, tanning industry consumes gallons of water. Therefore, for adopting green solvents in leather making, it is necessary to evaluate its influence on type I collagen, the major protein present in the skin matrix. The thermal stability of collagen from rat tail tendon fiber (RTT) treated with seven green solvents namely, ethanol, ethyl lactate, ethyl acetate, propylene carbonate, propylene glycol, polyethylene glycol-200 and heptane was determined using differential scanning calorimetry (DSC). Crosslinking efficiency of basic chromium sulfate and wattle on RTT in green solvents was determined. DSC thermograms show increase in thermal stability of RTT collagen against heat with green solvents (>78°C) compared to water (63°C). In the presence of crosslinkers, RTT demonstrated thermal stability >100°C in some green solvents, resulting in increased intermolecular forces between collagen, solvent and crosslinkers. The significant improvement in thermal stability of collagen potentiates the capability of green solvents as an alternative for water. Copyright © 2014 Elsevier B.V. All rights reserved.
Sirimamilla, P. Abhiram; Furmanski, Jevan; Rimnac, Clare M.
2012-01-01
The mechanism of crack initiation from a clinically relevant notch is not well-understood for crosslinked ultra high molecular weight polyethylene (UHMWPE) used in total joint replacement components. Static mode driving forces, rather than the cyclic mode conditions typically associated with fatigue processes, have been shown to drive crack propagation in this material. Thus, in this study, crack initiation in a notched specimen under a static load was investigated. A video microscope was used to monitor the notch surface of the specimen and crack initiation time was measured from the video by identifying the onset of crack initiation at the notch. Crack initiation was considered using a viscoelastic fracture theory. It was found that the mechanism of crack initiation involved both single layer and a distributed multi-layer phenomenon and that multi-layer crack initiation delayed the crack initiation time for all loading conditions examined. The findings of this study support that the viscoelastic fracture theory governs fracture mechanics in crosslinked UHMWPE. The findings also support that crack initiation from a notch in UHMWPE is a more complex phenomenon than treated by traditional fracture theories for polymers. PMID:23127638
SiRNA Crosslinked Nanoparticles for the Treatment of Inflammation-induced Liver Injury.
Tang, Yaqin; Zeng, Ziying; He, Xiao; Wang, Tingting; Ning, Xinghai; Feng, Xuli
2017-02-01
RNA interference mediated by small interfering RNA (siRNA) provides a powerful tool for gene regulation, and has a broad potential as a promising therapeutic strategy. However, therapeutics based on siRNA have had limited clinical success due to their undesirable pharmacokinetic properties. This study presents pH-sensitive nanoparticles-based siRNA delivery systems (PNSDS), which are positive-charge-free nanocarriers, composed of siRNA chemically crosslinked with multi-armed poly(ethylene glycol) carriers via acid-labile acetal linkers. The unique siRNA crosslinked structure of PNSDS allows it to have minimal cytotoxicity, high siRNA loading efficiency, and a stimulus-responsive property that enables the selective intracellular release of siRNA in response to pH conditions. This study demonstrates that PNSDS can deliver tumor necrosis factor alpha (TNF-α) siRNA into macrophages and induce the efficient down regulation of the targeted gene in complete cell culture media. Moreover, PNSDS with mannose targeting moieties can selectively accumulate in mice liver, induce specific inhibition of macrophage TNF-α expression in vivo, and consequently protect mice from inflammation-induced liver damages. Therefore, this novel siRNA delivering platform would greatly improve the therapeutic potential of RNAi based therapies.
Field Testing of Thermoplastic Encapsulants in High-Temperature Installations
Kempe, Michael D.; Miller, David C.; Wohlgemuth, John H.; ...
2015-11-01
Recently there has been increased interest in using thermoplastic encapsulant materials in photovoltaic modules, but concerns have been raised about whether these would be mechanically stable at high temperatures in the field. This has become a significant topic of discussion in the development of IEC 61730 and IEC 61215. We constructed eight pairs of crystalline-silicon modules and eight pairs of glass/encapsulation/glass thin-film mock modules using different encapsulant materials, of which only two were formulated to chemically crosslink. One module set was exposed outdoors with thermal insulation on the back side in Mesa, Arizona, in the summer (hot-dry), and an identicalmore » module set was exposed in environmental chambers. High-precision creep measurements (±20 μm) and electrical performance measurements indicate that despite many of these polymeric materials operating in the melt or rubbery state during outdoor deployment, no significant creep was seen because of their high viscosity, lower operating temperature at the edges, and/or the formation of chemical crosslinks in many of the encapsulants with age despite the absence of a crosslinking agent. Only an ethylene-vinyl acetate (EVA) encapsulant formulated without a peroxide crosslinking agent crept significantly. When the crystalline-silicon modules, the physical restraint of the backsheet reduced creep further and was not detectable even for the EVA without peroxide. Because of the propensity of some polymeric materials to crosslink as they age, typical thermoplastic encapsulants would be unlikely to result in creep in the vast majority of installations.« less
Electric Charge Accumulation in Polar and Non-Polar Polymers under Electron Beam Irradiation
NASA Astrophysics Data System (ADS)
Nagasawa, Kenichiro; Honjoh, Masato; Takada, Tatsuo; Miyake, Hiroaki; Tanaka, Yasuhiro
The electric charge accumulation under an electron beam irradiation (40 keV and 60 keV) was measured by using the pressure wave propagation (PWP) method in the dielectric insulation materials, such as polar polymeric films (polycarbonate (PC), polyethylene-naphthalate (PEN), polyimide (PI), and polyethylene-terephthalate (PET)) and non-polar polymeric films (polystyrene (PS), polypropylene (PP), polyethylene (PE) and polytetrafluoroethylene (PTFE)). The PE and PTFE (non-polar polymers) showed the properties of large amount of electric charge accumulation over 50 C/m3 and long saturation time over 80 minutes. The PP and PS (non-polar polymer) showed the properties of middle amount of charge accumulation about 20 C/m3 and middle saturation time about 1 to 20 minutes. The PC, PEN, PI and PET (polar polymers) showed the properties of small amount of charge accumulation about 5 to 20 C/m3 and within short saturation time about 1.0 minutes. This paper summarizes the relationship between the properties of charge accumulation and chemical structural formula, and compares between the electro static potential distribution with negative charged polymer and its chemical structural formula.
Synthesis and characterization of PEG-P(MAA-SS-VCL) nanoparticles
NASA Astrophysics Data System (ADS)
Yu, L. L.; Yang, K.; Mu, R. H.; Zhang, N.; Su, L.
2016-07-01
The PEG-P(MAA-SS-VCL) nanoparticles were obtained using disulfide containing dimethacrylate (SS) as cross-linking agent, using polyethylene glycol methyl acrylate (PEGMA), N-Vinyl-ε-caprolactam (VCL), and methacrylic acid (MAA) as monomers via homogeneous polymerization in aqueous. The PEG-P(MAA-SS-VCL) nanoparticles were characterized by FT-IR and TGA. The particle size and morphology variation in different environments were detected by dynamic light scattering (DLS) and scanning electron microscopy (SEM). It is the very method that PEG-P(MAA-SS-VCL) nanoparticles can be obtained in this study.
Tribology considerations for hip joint articulations in relation to the "new orthopaedic patient".
Rieker, C B
2006-01-01
The purpose of this review is to examine alternative bearings used in total hip arthroplasty (THA) and discuss the specific tribologic needs of the "New Orthopaedic Patient". As orthopaedic patients today are younger and more active, there is a clear need for hip joint implants and articulations minimising the amount of wear and guarantying better stability. Recent modern developments in tribology with highly cross-linked polyethylenes and hard-on-hard bearings allow the safe and effective use of larger diameter articulations in THA.
Large Metal Heads and Vitamin E Polyethylene Increase Frictional Torque in Total Hip Arthroplasty.
Meneghini, R Michael; Lovro, Luke R; Wallace, Joseph M; Ziemba-Davis, Mary
2016-03-01
Trunnionosis has reemerged in modern total hip arthroplasty for reasons that remain unclear. Bearing frictional torque transmits forces to the modular head-neck interface, which may contribute to taper corrosion. The purpose of this study is to compare frictional torque of modern bearing couples in total hip arthroplasty. Mechanical testing based on in vivo loading conditions was used to measure frictional torque. All bearing couples were lubricated and tested at 1 Hz for more than 2000 cycles. The bearing couples tested included conventional, highly crosslinked (XLPE) and vitamin E polyethylene, CoCr, and ceramic femoral heads and dual-mobility bearings. Statistical analysis was performed using Student t test for single-variable and analysis of variance for multivariant analysis. P ≤ .05 was considered statistically significant. Large CoCr metal heads (≥36 mm) substantially increased frictional torque against XLPE liners (P = .01), a finding not observed in ceramic heads. Vitamin E polyethylene substantially increased frictional torque compared with XLPE in CoCr and ceramic heads (P = .001), whereas a difference between conventional and XLPE was not observed (P = .69) with the numbers available. Dual-mobility bearing with ceramic inner head demonstrated the lowest mean frictional torque of all bearing couples. In this simulated in vivo model, large-diameter CoCr femoral heads and vitamin E polyethylene liners are associated with increased frictional torque compared with smaller metal heads and XLPE, respectively. The increased frictional torque of vitamin E polyethylene and larger-diameter femoral heads should be considered and further studied, along with reported benefits of these modern bearing couples. Copyright © 2016 Elsevier Inc. All rights reserved.
3D freeform printing of silk fibroin.
Rodriguez, Maria J; Dixon, Thomas A; Cohen, Eliad; Huang, Wenwen; Omenetto, Fiorenzo G; Kaplan, David L
2018-04-15
Freeform fabrication has emerged as a key direction in printing biologically-relevant materials and structures. With this emerging technology, complex structures with microscale resolution can be created in arbitrary geometries and without the limitations found in traditional bottom-up or top-down additive manufacturing methods. Recent advances in freeform printing have used the physical properties of microparticle-based granular gels as a medium for the submerged extrusion of bioinks. However, most of these techniques require post-processing or crosslinking for the removal of the printed structures (Miller et al., 2015; Jin et al., 2016) [1,2]. In this communication, we introduce a novel method for the one-step gelation of silk fibroin within a suspension of synthetic nanoclay (Laponite) and polyethylene glycol (PEG). Silk fibroin has been used as a biopolymer for bioprinting in several contexts, but chemical or enzymatic additives or bulking agents are needed to stabilize 3D structures. Our method requires no post-processing of printed structures and allows for in situ physical crosslinking of pure aqueous silk fibroin into arbitrary geometries produced through freeform 3D printing. 3D bioprinting has emerged as a technology that can produce biologically relevant structures in defined geometries with microscale resolution. Techniques for fabrication of free-standing structures by printing into granular gel media has been demonstrated previously, however, these methods require crosslinking agents and post-processing steps on printed structures. Our method utilizes one-step gelation of silk fibroin within a suspension of synthetic nanoclay (Laponite), with no need for additional crosslinking compounds or post processing of the material. This new method allows for in situ physical crosslinking of pure aqueous silk fibroin into defined geometries produced through freeform 3D printing. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Baykal, D.; Siskey, R.S.; Haider, H.; Saikko, V.; Ahlroos, T.; Kurtz, S.M.
2013-01-01
The introduction of numerous formulations of Ultra-high molecular weight polyethylene (UHMWPE), which is widely used as a bearing material in orthopedic implants, necessitated screening of bearing couples to identify promising iterations for expensive joint simulations. Pin-on-disk (POD) testers capable of multidirectional sliding can correctly rank formulations of UHMWPE with respect to their predictive in vivo wear behavior. However, there are still uncertainties regarding POD test parameters for facilitating clinically relevant wear mechanisms of UHMWPE. Studies on the development of POD testing were briefly summarized. We systematically reviewed wear rate data of UHMWPE generated by POD testers. To determine if POD testing was capable of correctly ranking bearings and if test parameters outlined in ASTM F732 enabled differentiation between wear behavior of various formulations, mean wear rates of non-irradiated, conventional (25–50 kGy) and highly crosslinked (≥90 kGy) UHMWPE were grouped and compared. The mean wear rates of non-irradiated, conventional and highly crosslinked UHMWPEs were 7.03, 5.39 and 0.67 mm3/MC. Based on studies that complied with the guidelines of ASTM F732, the mean wear rates of non-irradiated, conventional and highly crosslinked UHMWPEs were 0.32, 0.21 and 0.04 mm3/km, respectively. In both sets of results, the mean wear rate of highly crosslinked UHMPWE was smaller than both conventional and non-irradiated UHMWPEs (p<0.05). Thus, POD testers can compare highly crosslinked and conventional UHMWPEs despite different test parameters. Narrowing the allowable range for standardized test parameters could improve sensitivity of multi-axial testers in correctly ranking materials. PMID:23831149
Peak Stress Intensity Factor Governs Crack Propagation Velocity In Crosslinked UHMWPE
Sirimamilla, P. Abhiram; Furmanski, Jevan; Rimnac, Clare
2013-01-01
Ultra high molecular weight polyethylene (UHMWPE) has been successfully used as a bearing material in total joint replacement components. However, these bearing materials can fail as a result of in vivo static and cyclic loads. Crack propagation behavior in this material has been considered using the Paris relationship which relates fatigue crack growth rate, da/dN (mm/cycle) versus the stress intensity factor range, ΔK (Kmax-Kmin, MPa√m). However, recent work suggests that the crack propagation velocity of conventional UHMWPE is driven by the peak stress intensity (Kmax), not ΔK. The hypothesis of this study is that the crack propagation velocity of highly crosslinked and remelted UHMWPE is also driven by the peak stress intensity, Kmax, during cyclic loading, rather than by ΔK. To test this hypothesis, two highly crosslinked (65 kGy and 100 kGy) and remelted UHMWPE materials were examined. Frequency, waveform and R-ratio were varied between test conditions to determine the governing factor for fatigue crack propagation. It was found that the crack propagation velocity in crosslinked UHMWPE is also driven by Kmax and not ΔK, and is dependent on loading waveform and frequency in a predictable quasi-static manner. The current study supports that crack growth in crosslinked UHMWPE materials, even under cyclic loading conditions, can be described by a relationship between the velocity of crack growth, da/dt and the peak stress intensity, Kmax. The findings suggest that stable crack propagation can occur as a result of static loading only and this should be taken into consideration in design of UHMWPE total joint replacement components. PMID:23165898
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Qingkun; Frazier, Allister W.; Zhao, Xinpeng
Experimental realization of optically transparent, mechanically robust and flexible aerogels has been a longstanding challenge, which limits their practical applications in energy-saving devices, such as thermally insulating films for enhancing energy efficiency of windows. The poor transparency precluded even hypothetical consideration of the possibility of birefringent aerogels. We develop birefringent and optically isotropic aerogels that combine properties of thermal super-insulation, mechanical robustness and flexibility, and transparency to visible-spectrum light. This unusual combination of physical properties is achieved by combining liquid crystalline self-organization of cellulose nanofibers with polysiloxane cross-linking and control of the nanoscale porosity to form hybrid organic-inorganic mesostructured aerogels.more » Potential applications of these inexpensive materials range from single pane window retrofitting to smart fabrics.« less
Impact resistance and fractography in ultra high molecular weight polyethylenes.
Puértolas, J A; Pascual, F J; Martínez-Morlanes, M J
2014-02-01
Highly crosslinked ultra high molecular weight polyethylenes (UHMWPE) stabilized by a remelting process or by the addition of an antioxidant are highly wear resistant and chemically stable. However, these polyethylenes currently used in total joint replacements suffer a loss of mechanical properties, especially in terms of fracture toughness. In this study we analyze the impact behavior of different polyethylenes using an instrumented double notch Izod test. The materials studied are three resins: GUR1050, GUR1020 with 0.1wt% of vitamin E, and MG003 with 0.1wt% of vitamin E. These resins were gamma irradiated at 90kGy, and pre and post-irradiation remelting processes were applied to GUR1050 for two different time periods. Microstructural data were determined by means of differential scanning calorimetry and transmission electron microscopy. Fractography carried out on the impact fracture surfaces and images obtained by scanning electron microscopy after etching indicated the existence of a fringe structure formed by consecutive ductile-brittle and brittle-ductile transitions, which is related to the appearance of discontinuities in the load-deflection curves. A correlation has been made of the macroscopic impact strength results and the molecular chain and microstructural characteristics of these aforementioned materials, with a view to designing future resins with improved impact resistance. The use of UHMWPE resins with low molecular weight or the application of a remelting treatment could contribute to obtain a better impact strength behavior. © 2013 Published by Elsevier Ltd.
Poly(vinyl alcohol)-based film potentially suitable for antimicrobial packaging applications.
Musetti, Alessandro; Paderni, Katia; Fabbri, Paola; Pulvirenti, Andrea; Al-Moghazy, Marwa; Fava, Patrizia
2014-04-01
This work aimed at developing a thin and water-resistant food-grade poly(vinyl alcohol) (PVOH)-based matrix able to swell when in contact with high moisture content food products without rupturing to release antimicrobial agents onto the food surface. This film was prepared by blending PVOH and 7.20% (wt/wt of PVOH) of poly(ethylene glycol) (PEG) with citric acid as crosslinking agent. The film-forming solution was then casted onto a flat surface and the obtained film was 60 μm in thickness and showed a good transparency (close to T = 100%) in the visible region (400 to 700 nm). After immersion in water for 72 h at room temperature, the crosslinked matrix loses only 19.2% of its original weight (the percentage includes the amount of unreacted crosslinking agent, antimicrobial in itself). Water content, degree of swelling, and crosslinking density of the film prove that the presence of PEG diminishes the hydrophilic behavior of the material. Also the mechanical properties of the wet and dry film were assessed. Alongside this, 2.5% (wt/wt of dry film) of grapefruit seed extract (GSE), an antimicrobial agent, was added to the film-forming solution just before casting and the ability of the plastic matrix to release the additive was then evaluated in vitro against 2 GSE-susceptible microorganisms, Salmonella enteritidis and Listeria innocua. The results indicate that the developed matrix may be a promising food-grade material for the incorporation of active substances. © 2014 Institute of Food Technologists®
Ansari, Farzana; Chang, Jennifer; Huddleston, James; Van Citters, Douglas; Ries, Michael; Pruitt, Lisa
2013-12-01
Highly crosslinked ultra-high molecular weight polyethylene (UHMWPE) has shown success in reducing wear in hip arthroplasty but there remains skepticism about its use in Total Knee Replacement (TKR) inserts that are known to experience fatigue loading and higher local cyclic contact stresses. Two Legacy Posterior-Stabilized (LPS) Zimmer NexGen tibial implants sterilized by gamma irradiation in an inert environment with posts that fractured in vivo were analyzed. Failure mechanisms were determined using optical and scanning electron microscopy along with oxidative analysis via Fourier Transform Infra-Red (FTIR) spectroscopy. Micrographs of one retrieval revealed fatigue crack initiation on opposite sides of the post and quasi-brittle micromechanisms of crack propagation. FTIR of this retrieval revealed no oxidation. The fracture surface image of the second retrieval indicated a brittle fracture process and FTIR revealed oxidation in the explant. These two cases suggest that crosslinking of UHMWPE as a manufacturing process or sterilization method in conjunction with designs that incorporate high stress concentrations, such as the tibial post, may reduce material strength. Moreover, free radicals generated from ionizing radiation can render the polymer susceptible to oxidative embrittlement. Our findings suggest that tibial post fractures may be the results of in vivo oxidation and low level crosslinking. These and previous reports of fractured crosslinked UHMWPE devices implores caution when used with high stress concentrations, particularly when considering the potential for in vivo oxidation in TKR. Copyright © 2013 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
McKinnon, Daniel Devaud
This thesis focuses on studying the extension of motor axons through synthetic poly(ethylene glycol) PEG hydrogels that have been modified with biochemical functionalities to render them more biologically relevant. Specifically, the research strategy is to encapsulate embryonic stem cell-derived motor neurons (ESMNs) in synthetic PEG hydrogels crosslinked through three different chemistries providing three mechanisms for dynamically tuning material properties. First, a covalently crosslinked, enzymatically degradable hydrogel is developed and exploited to study the biophysical dynamics of axon extension and matrix remodeling. It is demonstrated that dispersed motor neurons require a battery of adhesive peptides and growth factors to maintain viability and extend axons while those in contact with supportive neuroglial cells do not. Additionally, cell-degradable crosslinker peptides and a soft modulus mimicking that of the spinal cord are requirements for axon extension. However, because local degradation of the hydrogel results in a cellular environment significantly different than that of the bulk, enzymatically degradable peptide crosslinkers were replaced with reversible covalent hydrazone bonds to study the effect of hydrogel modulus on axon extension. This material is characterized in detail and used to measure forces involved in axon extension. Finally, a hydrogel with photocleavable linkers incorporated into the network structure is exploited to explore motor axon response to physical channels. This system is used to direct the growth of motor axons towards co-cultured myotubes, resulting in the formation of an in vitro neural circuit.
Field Effect Transistor Behavior in Electrospun Polyaniline/Polyethylene Oxide Nanofibers
NASA Technical Reports Server (NTRS)
Miranda, Felix A.; Theofylaktos, Noulie; Mueller, Carl H.; Pinto, Nicholas J.
2004-01-01
Novel transistors and logic devices based on nanotechnology concepts are under intense development. The potential for ultra-low-power circuitry makes nanotechnology attractive for applications such as digital electronics and sensors. For NASA applications, nanotechnology offers tremendous opportunities for increased onboard data processing, and thus autonomous decision-making ability, and novel sensors that detect and respond to environmental stimuli with little oversight requirements. Polyaniline (PANi) is an intriguing material because its electrical conductivity can be changed from insulating to metallic by varying the doping levels and conformations of the polymer chain, and when combined with polyethylene oxide (PEO), can be formed into nanofibers with diameters ranging from approximately 50 to 500 nm (depending on the deposition conditions). The initial goal of this work was to demonstrate transistor behavior in these nanofibers, thus creating a foundation for future logic devices.
Pezzotti, Giuseppe; Zhu, Wenliang; Sugano, Nobuhiko; Marin, Elia; Yamamoto, Kengo; Nishiike, Naomichi; Hori, Tsubasa; Rondinella, Alfredo; McEntire, Bryan J; Bock, Ryan; Sonny Bal, B
2018-06-01
Experimental evidence demonstrates that a loss of stoichiometry at the surface of oxide bioceramic femoral heads enhances the oxidation rate of polyethylene acetabular liners in artificial hip joints. Contradicting the common notion that ceramics are bioinert, three independent experiments confirmed substantial chemical interactions between the ceramic femoral heads and their polyethylene counterparts. The experiments reported herein included hydrothermal tests, frictional tests, and hip-simulator experiments. It was discovered that oxide and non-oxide femoral heads differently affected the oxidation processes at the surface of the polyethylene liners, all other testing parameters being equal. Analytical data from X-ray photoelectron (XPS), cathodoluminescence (CL), Fourier-transform infrared (FTIR), and Raman spectroscopies unequivocally and consistently showed that the oxidation rate of polyethylene liners was greater when coupled with oxide as opposed to non-oxide ceramic heads. XPS analyses of O-Al-O bond fractions at the surface of a zirconia-toughened alumina (ZTA) short-term (20 months in vivo) femoral heads retrieval showed a ~50% reduction in favor of oxygen vacancy O-Al-V O and hydroxylated Al-O-H bonds. Off-stoichiometry drifts were confirmed in vitro under both static and dynamic conditions. They triggered oxidation and tangibly affected an advanced highly cross-linked sequentially irradiated and annealed ultra-high molecular weight polyethylene (UHMWPE) liner (increase in oxidation index up to ΔOI~1.2 after 5 × 10 5 cycles under dynamic swing conditions). Second-generation UHMWPE liners infused with vitamin E were also affected by the free flow of oxygen from the oxide femoral heads, although to a lesser extent. The fundamental findings of this study, which were also confirmed on retrievals, call for revised standards in material design and testing. Adopting these new criteria will provide an improved understanding of the importance of off-stoichiometry at the head/liner interface and may lead to significant extensions in artificial joint lifetimes. Copyright © 2018 Elsevier Ltd. All rights reserved.
Kelley, Keven M; Stenson, Alexandra C; Dey, Rajarashi; Whelton, Andrew J
2014-12-15
Green buildings are increasingly being plumbed with crosslinked polyethylene (PEX) potable water pipe. Tap water quality was investigated at a six month old plumbing system and chemical and odor quality impacts of six PEX pipe brands were examined. Eleven PEX related contaminants were found in the plumbing system; one regulated (toluene) and several unregulated: Antioxidant degradation products, resin solvents, initiator degradation products, or manufacturing aides. Water chemical and odor quality was monitored for new PEX-a, -b and -c pipes with (2 mg/L free chlorine) and without disinfectant over 30 days. Odor and total organic carbon (TOC) levels decreased for all pipes, but odor remained greater than the USA's Environmental Protection Agency's (USEPA) secondary maximum contaminant level. Odors were not attributed to known odorants ethyl-tert-butyl ether (ETBE) or methyl-tert-butyl ether (MTBE). Free chlorine caused odor levels for PEX-a1 pipe to increase from 26 to 75 threshold odor number (TON) on day 3 and affected the rate at which TOC changed for each brand over 30 days. As TOC decreased, the ultraviolet absorbance at 254 nm increased. Pipes consumed as much as 0.5 mg/L as Cl2 during each 3 day stagnation period. Sixteen organic chemicals were identified, including toluene, pyridine, methylene trichloroacetate and 2,4-di-tert-butylphenol. Some were also detected during the plumbing system field investigation. Six brands of PEX pipes sold in the USA and a PEX-a green building plumbing system impacted chemical and drinking water odor quality. Copyright © 2014 Elsevier Ltd. All rights reserved.
High temperature lined conduits, elbows and tees
De Feo, Angelo; Drewniany, Edward
1982-01-01
A high temperature lined conduit comprising, a liner, a flexible insulating refractory blanket around and in contact with the liner, a pipe member around the blanket and spaced therefrom, and castable rigid refractory material between the pipe member and the blanket. Anchors are connected to the inside diameter of the pipe and extend into the castable material. The liner includes male and female slip joint ends for permitting thermal expansion of the liner with respect to the castable material and the pipe member. Elbows and tees of the lined conduit comprise an elbow liner wrapped with insulating refractory blanket material around which is disposed a spaced elbow pipe member with castable refractory material between the blanket material and the elbow pipe member. A reinforcing band is connected to the elbow liner at an intermediate location thereon from which extend a plurality of hollow tubes or pins which extend into the castable material to anchor the lined elbow and permit thermal expansion. A method of fabricating the high temperature lined conduit, elbows and tees is also disclosed which utilizes a polyethylene layer over the refractory blanket after it has been compressed to maintain the refractory blanket in a compressed condition until the castable material is in place. Hot gases are then directed through the interior of the liner for evaporating the polyethylene and setting the castable material which permits the compressed blanket to come into close contact with the castable material.
NASA Technical Reports Server (NTRS)
Sullivan, Roy M.; Palko, Joseph L.; Tornabene, Robert T.; Bednarcyk, Brett A.; Powers, Lynn M.; Mital, Subodh K.; Smith, Lizalyn M.; Wang, Xiao-Yen J.; Hunter, James E.
2006-01-01
A series of engineering analysis studies were conducted to investigate the potential application of nanoclay-enhanced graphite/epoxy composites and polymer cross-linked silica aerogels in cryogenic hydrogen storage tank designs. This assessment focused on the application of these materials in spherical tank designs for unmanned aeronautic vehicles with mission durations of 14 days. Two cryogenic hydrogen tank design concepts were considered: a vacuum-jacketed design and a sandwiched construction with an aerogel insulating core. Analyses included thermal and structural analyses of the tank designs as well as an analysis of hydrogen diffusion to specify the material permeability requirements. The analyses also provided material property targets for the continued development of cross-linked aerogels and nanoclay-enhanced graphite/epoxy composites for cryogenic storage tank applications. The results reveal that a sandwiched construction with an aerogel core is not a viable design solution for a 14-day mission. A vacuum-jacketed design approach was shown to be far superior to an aerogel. Aerogel insulation may be feasible for shorter duration missions. The results also reveal that the application of nanoclay-enhanced graphite/epoxy should be limited to the construction of outer tanks in a vacuum-jacketed design, since a graphite/epoxy inner tank does not provide a significant weight savings over aluminum and since the ability of nanoclay-enhanced graphite/epoxy to limit hydrogen permeation is still in question.
Effects of 1 MeV electrons on the deformation mechanisms of polyethylene/carbon nanotube composites
NASA Astrophysics Data System (ADS)
Yang, Jianqun; Zhang, Xiaodong; Liu, Chaoming; Li, Xingji; Li, Hongxia; Ma, Guoliang; Tian, Feng
2017-10-01
Polymer nano-composites, especially in polyethylene (PE)/carbon nanotube (CNT) composites can be employed as radiation shielding and structural materials in space. When the PE/CNT composites are used in space, it is easy to suffer from radiation damage caused by charged particles. However, few studies about deformation mechanisms of the composites exposed to electron become available so far. In this paper, mutiwalled carbon nanotubes (MWCNTs) were incorporated into low density polyethylene (LDPE) with MWCNT loadings concentrations of 0.1 wt%. The structural evolution during uniaxial tensile deformation of the LDPE/0.1% MWCNT composites before and after 1 MeV electrons were investigated by means of a small angle X-ray scattering (SAXS) and wide angle X-ray diffraction (WAXD). Experimental results show that 1 MeV electrons obviously increase the ultimate tensile strength of the LDPE/MWCNT composites. From SAXS and WAXD analyses, it is shown that 1 MeV electrons inhibit the disintegration and the rotation of the lamellae, and slow down the formation of the new crystals. It is concluded that the intense interaction between MWCNTs and LDPE matrix and the crosslinking strengthening generated by 1 MeV electrons is the dominant reason for the changes of the deformation behaviors of LDPE.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Odian, G.; Bernstein, B.S.; Kelly, J.J.
1961-11-01
Gel contents can be obtained with polyethylene swollen with inhibitor- free allyl acrylate or inhibitor-free allyl methacrylate at a dose of only 0.05 Mrads Using Co/sup 60/ as the radiation source, allyl methacrylate gives higher gel content than allyl acrylate under similar conditions. icant and continues after Co/sup 60/ irradiation has been completed. Monomer desorption after a dose of 1.2 Mrads is less than after 0.05 Mrads, and does not continue after irradiation is stopped. Gel contents can be obtained without prior equilibrium swelling of polymer--monomer mixtures by irradiating the polymer in the presence of the monomer in a nitrogenmore » atmosphere. By irradiating under these conditions with prior equilibrium swelling, gel fractions appear to be higher than those normally obtained. Gel contents of irradiated equilibrium-swollen polyethylene/ allyl acrylate and polyethylene/allyl methacrylate increase with increasing radiation dose from 0.05 to 1.2 Mrads. Gel contents of 1.2 Mrad irradiated polyethyleneallyl methacrylate systems containing various initial amounts of monomer, increase with increasing monomer content. Polypropylene can be radiation crosslinked to give over 40% gel by prior equilibrium swelling with allyl acrylate or allyl methacrylate. (auth)« less
NASA Astrophysics Data System (ADS)
Maleki, Mahnam; Farzin, Mahmud; Mosaddegh, Peiman
2018-06-01
In this study, the effect of high density polyethylene (HDPE) and calcium carbonate (CaCO3) addition into constant amount of low density polyethylene/linear low density polyethylene (LDPE/LLDPE) matrix was investigated by using different mechanical and thermal parameters. Then, analysis of variance (ANOVA) was used to investigate the normal distribution of obtained data. Finally, sample containing 50 Phr of HDPE and 7 Phr of CaCO3 microparticles, was determined as optimized sample. The effect of different process parameters such as injecting back pressure, cooling and retention time, on mechanical and thermal properties of optimized sample was investigated as well. Also to investigate the effect of the number of recycling processes on the mechanical and thermal properties, two dominant degradation mechanisms were suggested. The first was the decreasing of chains molecular weight and formation of short length chains and the later was the formation of crosslinks and three dimensional networks. Results indicated that by increasing the number of recycling processes, crystallinity, melting point, modulus, strength at yielding point and toughness in comparison to pristine sample decreased at first and then showed an ascending trend. Elongation at break by increasing of the number of recycling processes, generally increased in comparison with initial sample.
Scott, Evan A.; Nichols, Michael D.; Cordova, Lee H.; George, Brandon J.; Jun, Young-Shin; Elbert, Donald L.
2008-01-01
Late-term thrombosis on drug-eluting stents is an emerging problem that might be addressed using extremely thin, biologically-active hydrogel coatings. We report a dip-coating strategy to covalently link poly(ethylene glycol) (PEG) to substrates, producing coatings with <≈100 nm thickness. Gelation of PEG-octavinylsulfone with amines in either bovine serum albumin (BSA) or PEG-octaamine was monitored by dynamic light scattering (DLS), revealing the presence of microgels before macrogelation. NMR also revealed extremely high end group conversions prior to macrogelation, consistent with the formation of highly crosslinked microgels and deviation from Flory-Stockmayer theory. Before macrogelation, the reacting solutions were diluted and incubated with nucleophile-functionalized surfaces. Using optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance with dissipation (QCM-D), we identified a highly hydrated, protein-resistant layer with a thickness of approximately 75 nm. Atomic force microscopy in buffered water revealed the presence of coalesced spheres of various sizes but with diameters less than about 100 nm. Microgel-coated glass or poly(ethylene terephthalate) exhibited reduced protein adsorption and cell adhesion. Cellular interactions with the surface could be controlled by using different proteins to cap unreacted vinylsulfone groups within the coating. PMID:18771802
Photodegradable, Photoadaptable Hydrogels via Radical-Mediated Disulfide Fragmentation Reaction.
Fairbanks, Benjamin D; Singh, Samir P; Bowman, Christopher N; Anseth, Kristi S
2011-04-26
Various techniques have been adopted to impart a biological responsiveness to synthetic hydrogels for the delivery of therapeutic agents as well as the study and manipulation of biological processes and tissue development. Such techniques and materials include polyelectrolyte gels that swell and deswell with changes in pH, thermosensitive gels that contract at physiological temperatures, and peptide cross-linked hydrogels that degrade upon peptidolysis by cell-secreted enzymes. Herein we report a unique approach to photochemically deform and degrade disulfide cross-linked hydrogels, mitigating the challenges of light attenuation and low quantum yield, permitting the degradation of hydrogels up to 2 mm thick within 120 s at low light intensities (10 mW/cm(2) at 365 nm). Hydrogels were formed by the oxidation of thiol-functionalized 4-armed poly(ethylene glycol) macromolecules. These disulfide cross-linked hydrogels were then swollen in a lithium acylphosphinate photoinitiator solution. Upon exposure to light, photogenerated radicals initiate multiple fragmentation and disulfide exchange reactions, permitting and promoting photodeformation, photowelding, and photodegradation. This novel, but simple, approach to generate photoadaptable hydrogels portends the study of cellular response to mechanically and topographically dynamic substrates as well as novel encapsulations by the welding of solid substrates. The principles and techniques described herein hold implications for more than hydrogel materials but also for photoadaptable polymers more generally.
Functionalized graphene oxide nanoparticles for cancer cell-specific delivery of antitumor drug.
Zhao, Xubo; Yang, Liangwei; Li, Xiaorui; Jia, Xu; Liu, Lei; Zeng, Jin; Guo, Jinshan; Liu, Peng
2015-01-21
The unique reduction-triggered functional graphene oxide nanoparticles (GON) with well-defined size and uniform distribution were designed as an innovative drug delivery platform for cancer treatment for the first time, via the redox radical polymerization of methacrylic acid from the polyethylene glycol (PEG) modified GON (GON-PEG), following by cross-linking with cystamine. Thermogravimetric analysis demonstrates that the typical PMAA2-GON-PEG carriers contain about 16 wt % PEG segments and 33 wt % poly(methacrylic acid) (PMAA) brushes. PEG moieties are incorporated to make the drug delivery platforms stealthy during blood circulation. Notably, introducing the cross-linked PMAA brushes efficiently minimizes the premature release of doxorubicin (DOX) in the stimulated normal tissues, and accelerates DOX release in the stimulated tumor tissues through response to reduce agent. The carriers showed a 6-fold faster releasing rate at pH 5.0 in the presence of 10 mM glutathione (GSH) (stimulated tumor tissues) than at pH 7.4 with 10 μM GSH (stimulated normal tissues). In vitro cytotoxicity test also showed that the cross-linked PMAA2-GON-PEG (CPMAA2-GON-PEG) carriers had remarkable cytocompatibility, and that the DOX-loaded CPMAA2-GON-PEG had excellent killing capability to SiHa cells.
Ahmed, Khalil
2015-11-01
Blends of acrylonitrile butadiene rubber/high density polyethylene (NBR/HDPE) compatibilized by Chloroprene rubber (CR) were prepared. A fixed quantity of industrial waste such as marble waste (MW, 40 phr) was also included. The effect of the blend ratio and CR on cure characteristics, mechanical and swelling properties of MW-filled NBR/HDPE blends was investigated. The results showed that the MW-filled NBR/HDPE blends revealed an increase in tensile strength, tear, modulus, hardness and cross-link density for increasing weight ratio of HDPE. The minimum torque (M L) and maximum torque (M H) of blends increased with increasing weight ratio of HDPE while scorch time (ts2) cure time (tc90), compression set and abrasion loss of blends decreased with increasing weight ratio of HDPE. The blends also showed a continuous reduction in elongation at break as well as swelling coefficient with increasing HDPE amount in blends. MW filled blends based on CR provided the most encouraging balance values of overall properties.
Ahmed, Khalil
2014-01-01
Blends of acrylonitrile butadiene rubber/high density polyethylene (NBR/HDPE) compatibilized by Chloroprene rubber (CR) were prepared. A fixed quantity of industrial waste such as marble waste (MW, 40 phr) was also included. The effect of the blend ratio and CR on cure characteristics, mechanical and swelling properties of MW-filled NBR/HDPE blends was investigated. The results showed that the MW-filled NBR/HDPE blends revealed an increase in tensile strength, tear, modulus, hardness and cross-link density for increasing weight ratio of HDPE. The minimum torque (ML) and maximum torque (MH) of blends increased with increasing weight ratio of HDPE while scorch time (ts2) cure time (tc90), compression set and abrasion loss of blends decreased with increasing weight ratio of HDPE. The blends also showed a continuous reduction in elongation at break as well as swelling coefficient with increasing HDPE amount in blends. MW filled blends based on CR provided the most encouraging balance values of overall properties. PMID:26644917
Cho, C S; Han, S Y; Ha, J H; Kim, S H; Lim, D Y
1999-04-30
Poly(ethylene glycol)(PEG) macromers terminated with acrylate groups and semi-interpenetrating polymer networks (SIPNs) composed of poly(epsilon-caprolactone)(PCL) and PEG macromer were synthesized to obtain a bioerodible hydrogel. Polymerization of PEG macromer resulted in the formation of cross-linked gels due to the multifunctionality of macromer. Glass transition temperature (Tg) and melting temperature (Tm) of PEG networks and PCL in the SIPNs were inner-shifted, indicating an interpenetration of PCL and PEG chains. Water content in the SIPNs increased with increasing PEG weight fraction due to the hydrophilicity of PEG. The amount of clonazepam (CNZ) released from the SIPNs increased with higher content in the SIPNs, lower drug loading, lower concentration of PEG macromer during the SIPNs preparation, and higher molecular weight of PEG. In particular, a combination with low PEG content and low CNZ solubility in water led to long-term constant release from these matrices in vitro and in vivo. Copyright.
Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Feng, Jiwen
2017-01-01
Abstract It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self‐catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte (C‐PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li+ and considerable ionic conductivity of 8.9 × 10−5 S cm−1 at ambient temperature. Moreover, the LiFePO4/C‐PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self‐catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes. PMID:29201612
NASA Astrophysics Data System (ADS)
Duan, S. H.; Kai, T.; Chowdhury, F. A.; Taniguchi, I.; Kazama, S.
2018-01-01
Poly(amidoamine) (PAMAM) dendrimers were incorporated into cross-linked poly(ethylene glycol) (PEGDMA) matrix to improve carbon dioxide (CO2) separation performance at elevated pressures. In our previous studies, PAMAM/PEGDMA hybrid membranes showed high CO2 separation properties from CO2/H2 mixed gases. In this study, proline, choline and ionic liquid [Choline][Pro] compounds were selected as rate promoters that were used to prepare PAMAM/PEGDMA hybrid membranes. The effect of addition of proline, choline, IL [Choline][Pro] on separation performance of PAMAM/PEGDMA) hybrid membranes for CO2/H2 separation was investigated. Amino acid proline, choline, and IL [Choline][Pro] were used to promote CO2 and amine reaction. With the addition of [Choline][Pro] into PAMAM/PEG membrane, CO2 permeance of PAMAM/PEG hybrid membranes are increased up to 46% without any change of selectivity of membrane for CO2.
Warenda, Monika; Richter, Anne; Schmidt, Diana; Janke, Andreas; Müller, Martin; Simon, Frank; Zimmermann, Ralf; Eichhorn, Klaus-Jochen; Voit, Brigitte; Appelhans, Dietmar
2012-09-14
For using successful (ultra)thin dendritic macromolecule films in (bio)sensing and microfluidic devices and for obtaining reproducible film properties, alteration effects arising from precoatings have to be avoided. Here, oligosaccharide-modified hyperbranched poly(ethylene imine)s (PEI-OS) were used to fabricate very thin PEI-OS films (15-20 nm in dry state), cross-linked with citric acid under condensation, and vacuum condition. However, no reactive precoating is necessary to obtain stable films, which allows very simple film preparation and avoids alteration of the PEIS-OS film properties arising from precoating. Several methods [(in situ) ellipsometry, AFM, XPS, (in situ) ATR-IR, streaming potential measurements] were applied to characterize homogeneity, surface morphology, and stability of these PEI-OS films between pH 2 and pH 10, but also the low protein adsorption behavior. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Zhao, Lingling; Niu, Lijing; Liang, Hongze; Tan, Hui; Liu, Chaozong; Zhu, Feiyan
2017-11-01
pH and glucose dual-responsive injectable hydrogels were prepared through the cross-linking of Schiff's base and phenylboronate ester using phenylboronic-modified chitosan, poly(vinyl alcohol) and benzaldehyde-capped poly(ethylene glycol). Protein drugs and live cells could be incorporated into the hydrogels during the in situ cross-linking, displaying sustained and pH/glucose-triggered drug release from the hydrogels and cell viability and proliferation in the three-dimensional hydrogel matrix as well. Hence, the hydrogels with insulin and fibroblasts were considered as bioactive dressings for diabetic wound healing. A streptozotocin-induced diabetic rat model was used to evaluate the efficacy of hydrogel dressings in wound repair. The results revealed that the incorporation of insulin and L929 in the hydrogels could promote neovascularization and collagen deposition and enhance the wound-healing process of diabetic wounds. Thus, the drug- and cell-loaded hydrogels have promising potential in wound healing as a medicated system for various therapeutic proteins and live cells.
Fu, Xinjian; Yang, Yang; Wang, Ningxia; Wang, Hong; Yang, Yajiang
2007-01-01
N-Stearine-N'-stearyl-L-phenylalanine, a chiral compound, was synthesized and used as a gelator for the gelation of polymerizable solvents, such as ss-hydroxyethyl methacrylate (HEMA), styrene, etc. The scanning electron microscope (SEM) images of the gelator aggregates show fibril-like helices, typical chiral aggregates with diameters of 100-200 nm. The solvent molecules were immobilized by capillary forces in the three-dimensional network structures of the organogels. The HEMA organogels containing crosslinker polyethylene glycol dimethacrylates (PEG200DMA) were subsequently polymerized by in situ UV irradiation. A porous polymerized organogels were obtained after removal of gelator aggregates through ethanol extraction. The chiral separation of D- and L-phenylalanine was carried out by the adsorption of the polymerized organogels. The adsorption efficiency of L-phenylalanine on the polymerized organogels was found to be dependent on the concentration of the gelator and crosslinker. (c) 2007 John Wiley & Sons, Ltd.
Ibricevic, Aida; Guntsen, Sean P.; Zhang, Ke; Shrestha, Ritu; Liu, Yongjian; Sun, Jing Yi; Welch, Michael J.; Wooley, Karen L.; Brody, Steven L.
2013-01-01
The airway provides a direct route for administration of nanoparticles bearing therapeutic or diagnostic payloads to the lung, however optimization of nanoplatforms for intracellular delivery remains challenging. Poly(ethylene glycol) (PEG) surface modification improves systemic performance but less is known about PEGylated nanoparticles administered to the airway. To test this, we generated a library of cationic, shell crosslinked knedel-like nanoparticles (cSCKs), including PEG (1.5 kDa PEG; 2, 5, 10 molecules/polymer arm) on the outer shell. Delivery of PEGylated cSCK to the mouse airway showed significantly less inflammation in a PEG dose-dependent manner. PEGylation also enhanced the entry of cSCKs in lung alveolar epithelial cells and improved surfactant penetration. The PEGylation effect could be explained by the altered mechanism of endocytosis. While non-PEGylated cSCKs used the clathrin-dependent route for endocytosis, entry of PEGylated cSCK was clathrin-independent. Thus, nanoparticle surface modification with PEG represents an advantageous design for lung delivery. PMID:23453959
Minnesota retrofit insulation in situ test program
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1978-06-01
The use of cellulose, glass fiber, rock/slag fiber and urea formaldehyde installed as retrofit insulation materials in residential walls and ceilings was studied. Homes were selected for testing according to the type of retrofit insulation, age of retrofit insulation and whether the retrofit was in the wall or ceiling. The total project was comprised of 22 wall and 48 ceiling samples. Samples of retrofit insulation were taken from an area of three to four square feet in the ceiling or wall of the home. The sample volume was measured, the sample removed and double-sealed in polyethylene bags. The samples weremore » shipped to the laboratory for testing. Laboratory measurements were made of density, moisture content, thermal resistance, and relative flammability of each sample. Additionally, the friability and compressive strength of each urea-formaldehyde foam sample was measured. The following results were obtained. Cellulosic loose fill insulation tests indicated that settling and moisture build-up are not serious problems. Flammability is a concern. Age did not affect the properties of the cellulosic loose fill, but fungal growth was evident. Shrinkage, ranging from 2.5 to 9 percent, averaging 4.5 percent, was exhibited. Degradation of the foam samples with time did not occur. Density was the most critical property affecting the other properties. The higher the density, the higher the thermal resistence per inch, the lower the friability and the higher the compressive strength. The accurate prediction of the fiber diameter, amount of unfiberized mineral, and extent of modular clumping thermal resistance of loose fill mineral fiber insulations is related to and is not solely a factor of density. The materials in this sample did not noticeably affect the structure or wiring of the retrofitted homes. (LCL)« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pallesen, T.R.; Braestrup, M.W.; Jorgensen, O.
Development of Danish North Sea hydrocarbon resources includes the 17-km Rolf pipeline installed in 1985. This one consists of an insulated 8-in. two-phase flow product line with a 3-in. piggyback gas lift line. A practical solution to design of this insulated pipeline, including the small diameter, piggyback injection line was corrosion coating of fusion bonded epoxy (FBE) and polyethylene (PE) sleeve pipe. The insulation design prevents hydrate formation under the most conservative flow regime during gas lift production. Also, the required minimum flow rate during the initial natural lift period is well below the value anticipiated at the initiation ofmore » gas lift. The weight coating design ensures stability on the seabed during the summer months only; thus trenching was required during the same installation season. Installation of insulated flowlines serving marginal fields is a significant feature of North Sea hydrocarbon development projects. The Skjold field is connected to Gorm by a 6-in., two-phase-flow line. The 11-km line was installed in 1982 as the first insulated pipeline in the North Sea. The Rolf field, located 17 km west of Gorm, went on stream Jan. 2. The development includes an unmanned wellhead platform and an insulated, two-phase-flow pipeline to the Gorm E riser platform. After separation on the Gorm C process platform, the oil and condensate are transported to shore through the 20-in. oil pipeline, and the natural gas is piped to Tyra for transmission through the 30-in. gas pipeline. Oil production at Rolf is assisted by the injection of lift gas, transported from Gorm through a 3-in. pipeline, installed piggyback on the insulated 8-in. product line. The seabed is smooth and sandy, the water depth varying between 33.7 m (110.5 ft) at Rolf and 39.1 m (128 ft) at Gorm.« less
The USML-1 wire insulation flammability glovebox experiment
NASA Technical Reports Server (NTRS)
Greenberg, Paul S.; Sacksteder, Kurt R.; Kashiwagi, Takashi
1995-01-01
Flame spreading tests have been conducted using thin fuels in microgravity where buoyant convection is suppressed. In spacecraft experiments flames were ignited in quiescent atmospheres with an elevated oxygen content, demonstrating that diffusional mechanisms can be sufficient alone to sustain flame spreading. In ground-based facilities (i.e. drop towers and parabolic aircraft) low-speed convection sustains flames at much lower concentrations of atmospheric oxygen than in quiescent microgravity. Ground-based experiments are limited to very thin fuels (e.g., tissue paper); practical fuels, which are thicker, require more test time than is available. The Glovebox Facility provided for the USML 1 mission provided an opportunity to obtain flame spreading data for thicker fuel Herein we report the results from the Wire Insulation Flammability (WIF) Experiment performed in the Glovebox Facility. This experiment explored the heating, ignition and burning of 0.65 mm thick polyethylene wire insulation in low-speed flows in a reduced gravity environment. Four tests were conducted, two each in concurrent flow (WIF A and C) and opposed flow (WIF B and D), providing the first demonstration of flame spreading in controlled forced convection conducted in space.
Taniguchi, N; Jinno, T; Takada, R; Koga, D; Ando, T; Okawa, A; Haro, H
2018-05-01
The use of screws and the presence of screw holes may cause acetabular osteolysis and implant loosening in cementless total hip arthroplasty (THA) using conventional polyethylene. In contrast, this issue is not fully understood using highly crosslinked polyethylene (HXLPE), particularly in large comparative study. Therefore, we performed a case-control study to assess the influence of screw usage and screw holes on: (1) implant fixation and osteolysis and (2) polyethylene steady-state wear rate, using cases with HXLPE liners followed up for 7-10 years postoperatively. The screw usage and screw holes adversely affect the implant fixation and incidence of wear-related osteolysis in THA with HXLPE. We reviewed 209 primary cementless THAs performed with 26-mm cobalt-chromium heads on HXLPE liners. To compare the effects of the use of screws and the presence of screw holes, the following groups were established: (1) with-screw (n=140); (2) without-screw (n=69); (3) no-hole (n=27) and (4) group in which a cup with screw holes, but no screw was used (n=42). Two adjunct groups (no-hole cups excluded) were established to compare the differences in the two types of HXLPE: (5) remelted group (n=100) and (6) annealed group (n=82). Implant stability and osteolysis were evaluated by plain radiography and computed tomography. The wear rate from 1 year to the final evaluation was measured using plain X-rays and PolyWare Digital software. All cups and stems achieved bony fixation. On CT-scan, no acetabular osteolysis was found, but there were 3 cases with a small area of femoral osteolysis. The mean steady-state wear rate of each group was (1) 0.031±0.022, (2) 0.033±0.035, (3) 0.031±0.024, (4) 0.029±0.018, (5) 0.030±0.018 and (6) 0.034±0.023mm/year, respectively. A comparison of the effects of screw usage or screw holes found no significant between-group differences in the implant stability, prevalence of osteolysis [no acetabular osteolysis and 3/209 at femoral side (1.4%)] and steady-state wear rate. This study suggests that there are no adverse effects on the results of THA with HXLPE from the use of cups with screw holes and the use of screws for cup fixation. Level III retrospective case-control study. Copyright © 2018 Elsevier Masson SAS. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Juhasz, Z.; Sulik, B.; Racz, R.
2010-12-15
A relatively large yield of neutralized atoms was observed when 3 keV Ar{sup 7+} ions were guided trough polyethylene terephthalate nanocapillaries. Time and deposited-charge dependence of the angular distribution of both the guided ions and the neutrals was measured simultaneously using a two-dimensional multichannel plate detector. The yield of neutrals increased significantly faster than that of guided ions and saturated typically at a few percent level. In accordance with earlier observations, both the yield and the mean emission angle of the guided ions exhibited strong oscillations. For the atoms, the equilibrium was achieved not only faster, but also without significantmore » oscillations in yield and angular position. A phase analysis of these time dependencies provides insight into the dynamic features of the self-organizing mechanisms, which leads to ion guiding in insulating nanocapillaries.« less
Synthesis and Properties of Cross-Linked Polyamide Aerogels
NASA Technical Reports Server (NTRS)
Williams, Jarrod C.; Meador, Mary Ann; McCorkle, Linda
2015-01-01
We report the first synthesis of cross-linked polyamide aerogels through step growth polymerization using a combination of diamines, diacid chloride and triacid chloride. Polyamide oligomers endcapped with amines are prepared as stable solutions in N-methylpyrrolidinone from several different diamine precursors and 1,3-benzenedicarbonyl dichloride. Addition of 1,3,5-benzenetricarbonyl trichloride yields gels which form in under five minutes according to the scheme shown. Solvent exchange of the gels into ethanol, followed by drying using supercritical CO2 extraction gives colorless aerogels with densities around 0.1 to 0.2 gcm3. Thicker monolithes of the polyamide aerogels are stiff and strong, while thin films of certain formulations are highly flexible, durable, and even translucent. These materials may have use as insulation for deployable space structures, rovers, habitats or extravehicular activity suits as well as in many terrestrial applications. Strucure property relationships of the aerogels, including surface area, mechanical properties, and thermal conductivity will be discussed.
1985-06-01
evaporated onto the resulting films. These films were then cut to form disks about 8 mm in diameter and 0.7 mm thick. While one electrode covered the full...surrounded by a heating coil, inside an airtight chamber. A spring loaded brass electrode presses the sample and the other electrode ." down onto the copper...cylinder. A sapphire disk insulates the lower " lectrodh( from the copper. This arrangement guarantees good thermal contact, arid electrical
Diisocyanate mediated polyether modified gelatin drug carrier for controlled release
Vijayakumar, Vediappan; Subramanian, Kaliappagounder
2013-01-01
Gelatin is an extensively studied biopolymer hydrogel drug carrier due to its biocompatibility, biodegradability and non-toxicity of its biodegraded products formed in vivo. But with the pristine gelatin it is difficult to achieve a controlled and desirable drug release characteristics due to its structural and thermal lability and high solubility in aqueous biofluids. Hence it is necessary to modify its solubility and structural stability in biofluids to achieve controlled release features with improved drug efficacy and broader carrier applications. In the present explorations an effort is made in this direction by cross linking gelatin to different extents using hitherto not studied isocyanate terminated poly(ether) as a macrocrosslinker prepared from poly(ethylene glycol) and isophorone diisocyanate in dimethyl sulfoxide. The crosslinked samples were analyzed for structure by Fourier transform-infrared spectroscopy, thermal behavior through thermogravimetric analysis and differential scanning calorimetry. The cross linked gelatins were biodegradable, insoluble and swellable in biofluids. They were evaluated as a carrier for in vitro drug delivery taking theophylline as a model drug used in asthma therapy. The crosslinking of gelatin decreased the drug release rate by 10–20% depending upon the extent of crosslinking. The modeled drug release characteristics revealed an anomalous transport mechanism. The release rates for ampicillin sodium, 5-fluorouracil and theophylline drugs in a typical crosslinked gelatin carrier were found to depend on the solubility and hydrophobicity of the drugs, and the pH of the fluid. The observed results indicated that this material can prove its mettle as a viable carrier matrix in drug delivery applications. PMID:24493973
ac aging and space-charge characteristics in low-density polyethylene polymeric insulation
NASA Astrophysics Data System (ADS)
Chen, G.; Fu, M.; Liu, X. Z.; Zhong, L. S.
2005-04-01
In the present work efforts have been made to investigate the influence of ac aging on space-charge dynamics in low-density polyethylene (LDPE). LDPE films with 200 μm were aged under various electric stress levels at 50 Hz for various times at ambient temperature. Space-charge dynamics in the samples after aging were monitored using the pulsed electroacoustic technique. It has been revealed that the space charge under ac aging conditions is related to the level of the applied field, duration of the voltage application, as well as the electrode materials. By comparing with the results of unaged sample the results from aged sample provide a direct evidence of changing trapping characteristics after ac aging. Negative space charge is present in the bulk of the material and the total amount of charge increases with the aging time. The amount of charge increases with the applied field. Charge decay test indicates that the charges are captured in deep traps. These deep traps are believed to form during the aging and related to change caused by injected charge. By using different electrode materials such as gold, brass alloy, and polyethylene loaded with carbon black, it was found that the electrode has an important role in the formation of charge, hence subsequent changes caused by charge. The charge dynamics of the aged samples under dc bias differ from the sample without ac aging, indicating changes brought in by ac aging. Chemical analysis by Fourier transform infrared spectroscope and Raman microscope reveals no detectable chemical changes taken place in the bulk of the material after ac aging. Finally, the consequence of the accumulation of space charge under ac conditions on the lifetime of the material has been discussed. The presence of deeply trapped space charge leads to an electric stress enhancement which may shorten the lifetime of the insulation system.
The evolution of and challenges for industrial radiation processing—2012
NASA Astrophysics Data System (ADS)
Berejka, A. J.; Cleland, M. R.; Walo, M.
2014-01-01
The evolution of industrial radiation processing is traced from Roentgen's discovery of X-radiation in 1895 by following the development of high current, electron beam accelerators (EB) throughout the twentieth century. Although Becquerel soon followed Roentgen with his discovery of what became to be known as radioactivity, electrical sources for ionizing radiation dominate industrial processing with there being more than ten times as many industrial installations using high current EB equipment than the facilities relying upon large concentrations of radioactive isotopes. In the 1950s, the discovery that ionizing radiation would enhance the value of what has become the world's largest volume commodity plastic, polyethylene (PE), opened the way for full scale commercial use of high current EB equipment. While the crosslinking of the PE insulation on wire became one of the first major industrial applications, other uses of EB processing soon followed. In the 1970s, low-energy, self-shielded EB equipment made the surface curing of inks, coatings and adhesives more industrially viable. In the early part of the twenty-first century, new market applications involving the low-energy EB surface decontamination of packaging materials emerged. This new area poses challenges for the metrology needed to control industrial processes, in that there is limited EB penetration into what have been used as dosimeters by industry. Major industrial use of radiation process is now over 50 years old. Because of the diversity of end-uses and the fact that the use of ionizing radiation in industry is a process technique, it is hard to quantify the value-added to numerous commercial products that benefit from this energy efficient process. It may be in excess of a trillion Euros in value-added to articles of commerce. In this milieu, there are some broad-based opportunities for research which are noted.
Kwon, Jeong Hyun; Park, Junhong; Lee, Myung Keun; Park, Jeong Woo; Jeon, Yongmin; Shin, Jeong Bin; Nam, Minwoo; Kim, Choong-Ki; Choi, Yang-Kyu; Choi, Kyung Cheol
2018-05-09
The lack of reliable, transparent, and flexible electrodes and insulators for applications in thin-film transistors (TFTs) makes it difficult to commercialize transparent, flexible TFTs (TF-TFTs). More specifically, conventional high process temperatures and the brittleness of these elements have been hurdles in developing flexible substrates vulnerable to heat. Here, we propose electrode and insulator fabrication techniques considering process temperature, transmittance, flexibility, and environmental stability. A transparent and flexible indium tin oxide (ITO)/Ag/ITO (IAI) electrode and an Al 2 O 3 /MgO (AM)-laminated insulator were optimized at the low temperature of 70 °C for the fabrication of TF-TFTs on a polyethylene terephthalate (PET) substrate. The optimized IAI electrode with a sheet resistance of 7 Ω/sq exhibited the luminous transmittance of 85.17% and maintained its electrical conductivity after exposure to damp heat conditions because of an environmentally stable ITO capping layer. In addition, the electrical conductivity of IAI was maintained after 10 000 bending cycles with a tensile strain of 3% because of the ductile Ag film. In the metal/insulator/metal structure, the insulating and mechanical properties of the optimized AM-laminated film deposited at 70 °C were significantly improved because of the highly dense nanolaminate system, compared to those of the Al 2 O 3 film deposited at 70 °C. In addition, the amorphous indium-gallium-zinc oxide (a-IGZO) was used as the active channel for TF-TFTs because of its excellent chemical stability. In the environmental stability test, the ITO, a-IGZO, and AM-laminated films showed the excellent environmental stability. Therefore, our IGZO-based TFT with IAI electrodes and the 70 °C AM-laminated insulator was fabricated to evaluate robustness, transparency, flexibility, and process temperature, resulting in transfer characteristics comparable to those of an IGZO-based TFT with a 150 °C Al 2 O 3 insulator.
Effect Of Low External Flow On Flame Spreading Over ETFE Insulated Wire Under Microgravity
NASA Technical Reports Server (NTRS)
Nishizawa, Katsuhiro; Fujita, Osamu; Ito, Kenichi; Kikuchi, Masao; Olson, Sandra L.; Kashiwagi, Takashi
2003-01-01
Fire safety is one of the most important issues for manned space missions. A likely cause of fires in spacecraft is wire insulation combustion in electrical system. Regarding the wire insulation combustion it important to know the effect of low external flow on the combustion because of the presence of ventilation flow in spacecraft. Although, there are many researches on flame spreading over solid material at low external flows under microgravity, research dealing with wire insulation is very limited. An example of wire insulation combustion in microgravity is the Space Shuttle experiments carried out by Greenberg et al. However, the number of experiments was very limited. Therefore, the effect of low flow velocity is still not clear. The authors have reported results on flame spreading over ETFE (ethylene - tetrafluoroetylene) insulated wire in a quiescent atmosphere in microgravity by 10 seconds drop tower. The authors also performed experiments of polyethylene insulated nichrom wire combustion in low flow velocity under microgravity. The results suggested that flame spread rate had maximum value in low flow velocity condition. Another interesting issue is the effect of dilution gas, especially CO2, which is used for fire extinguisher in ISS. There are some researches working on dilution gas effect on flame spreading over solid material in quiescent atmosphere in microgravity. However the research with low external flow is limited and, of course, the research discussing a relation of the appearance of maximum wire flammability in low flow velocity region with different dilution gas cannot be found yet. The present paper, therefore, investigates the effect of opposed flow with different dilution gas on flame spreading over ETFE insulated wire and change in the presence of the maximum flammability depending on the dilution gas type is discussed within the limit of microgravity time given by ground-based facility.
NASA Technical Reports Server (NTRS)
Leventis, Nicholas
2005-01-01
In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect orders-of-magnitude increase in strength, nevertheless, by varying the polymer we expect to impart other properties such as hydrophobicity, thermal stability and perhaps electrical conductivity. Besides polymers, crosslinkers will include metals and ceramics (e.g., through POSS precursors). Finally, network morphology directs load dissipation, and of approximately 30 different crosslinked oxide aerogels, vanadia, whose structure is fibrous rather than particulate, yields a much stronger (by 4..) material than silica of the same density. It seems imperative to implement control of network morphology, even through templating.
The Survival of Total Knee Arthroplasty: Current Data from Registries on Tribology: Review Article.
Civinini, Roberto; Carulli, Christian; Matassi, Fabrizio; Lepri, Andrea Cozzi; Sirleo, Luigi; Innocenti, Massimo
2017-02-01
Polyethylene (PE) wear is a major contributor to implant loosening following total knee arthroplasty (TKA), and advanced bearings in TKA are being investigated with hopes of reducing or eliminate wear-related loosening. Currently, information on knee tribology is available from national joint registries and may be the best tools to evaluate the efficacy and safety of design innovations in joint arthroplasty. We performed a review of national joint registries trying to answer the following questions: "Which is the main factor directly related to revisions rate in TKA?" and "Are there new bearing options better than conventional ones?" A review was performed of all published annual reports of National Joint Registers, as well as of the literature. The search was carried out using and comparing the National Joint Registers. Current data from registries for total knee arthroplasty indicates that age is the major factor affecting the outcome of primary total knee replacement. The 10-year cumulative revision rate for non-cross-linked PE was 5.8% and for XLPE it was 3.5%. The effect of cross-linked polyethylene was more evident in the younger patients. The survival of the oxidized zirconium (OxZr) femoral component appears better when compared to a similar age group of patients with conventional group of prostheses. Our review suggests that the revision rates are half for the OxZr components compared to conventional CoCr femoral components. Age is the most relevant single factor related to revision rate. Cross-linked PE has a statistical lower revision rate at 10 years compared to conventional PE and, in the OxZr group, the revision rate is 2 times lower than Co-Cr in the same group of age.
Rajan, Sujata Sundara; Turovskiy, Yevgeniy; Singh, Yashveer; Chikindas, Michael L.; Sinko, Patrick J.
2014-01-01
Women with bacterial vaginosis (BV) display reduced vaginal acidity, which make them susceptible to associated infections such as HIV. In the current study, poly(ethylene glycol) (PEG) nanocarrier-based degradable hydrogels were developed for the controlled release of lactic acid in the vagina of BV-infected women. PEG-lactic acid (PEG-LA) nanocarriers were prepared by covalently attaching lactic acid to 8-arm PEG-SH via cleavable thioester bonds. PEG-LA nanocarriers with 4 copies of lactic acid per molecule provided controlled release of lactic acid with a maximum release of 23% and 47% bound lactic acid in phosphate buffered saline (PBS, pH 7.4) and acetate buffer (AB, pH 4.3), respectively. The PEG nanocarrier-based hydrogels were formed by cross-linking the PEG-LA nanocarriers with 4-arm PEG-NHS via degradable thioester bonds. The nanocarrier-based hydrogels formed within 20 min under ambient conditions and exhibited an elastic modulus that was 100-fold higher than the viscous modulus. The nanocarrier-based degradable hydrogels provided controlled release of lactic acid for several hours; however, a maximum release of only 10%–14% bound lactic acid was observed possibly due to steric hindrance of the polymer chains in the cross-linked hydrogel. In contrast, hydrogels with passively entrapped lactic acid showed burst release with complete release within 30 min. Lactic acid showed antimicrobial activity against the primary BV pathogen Gardnerella vaginalis with a minimum inhibitory concentration (MIC) of 3.6 mg/ml. In addition, the hydrogels with passively entrapped lactic acid showed retained antimicrobial activity with complete inhibition G. vaginalis growth within 48 h. The results of the current study collectively demonstrate the potential of PEG nanocarrier-based hydrogels for vaginal administration of lactic acid for preventing and treating BV. PMID:25223229
Multipurpose hardened spacecraft insulation
NASA Technical Reports Server (NTRS)
Steimer, Carlos H.
1990-01-01
A Multipurpose Hardened Spacecraft Multilayer Insulation (MLI) system was developed and implemented to meet diverse survivability and performance requirements. Within the definition and confines of a MLI assembly (blanket), the design: (1) provides environmental protection from natural and induced nuclear, thermal, and electromagnetic radiation; (2) provides adequate electrostatic discharge protection for a geosynchronous satellite; (3) provides adequate shielding to meet radiated emission needs; and (4) will survive ascent differential pressure loads between enclosed volume and space. The MLI design is described which meets these requirements and design evolution and verification is discussed. The application is for MLI blankets which closeout the area between the laser crosslink subsystem (LCS) equipment and the DSP spacecraft cabin. Ancillary needs were implemented to ease installation at launch facility and to survive ascent acoustic and vibration loads. Directional venting accommodations were also incorporated to avoid contamination of LCS telescope, spacecraft sensors, and second surface mirrors (SSMs).
Effects of thermal and electrical stressing on the breakdown behavior of space wiring
NASA Technical Reports Server (NTRS)
Hammoud, Ahmad; Stavnes, Mark; Suthar, Jayant; Laghari, Javaid
1995-01-01
Several failures in the electrical wiring systems of many aircraft and space vehicles have been attributed to arc tracking and damaged insulation. In some instances, these failures proved to be very costly as they have led to the loss of many aircraft and imperilment of space missions. Efforts are currently underway to develop lightweight, reliable, and arc track resistant wiring for aerospace applications. In this work, six wiring constructions were evaluated in terms of their breakdown behavior as a function of temperature. These hybrid constructions employed insulation consisting of Kapton, Teflon, and cross-linked Tefzel. The properties investigated included the 400 Hz AC dielectric strength at ambient and 200 C, and the lifetime at high temperature with an applied bias of 40, 60, and 80% of breakdown voltage level. The results obtained are discussed, and conclusions are made concerning the suitability of the wiring constructions investigated for aerospace applications.
Effects of thermal and electrical stressing on the breakdown behavior of space wiring
NASA Astrophysics Data System (ADS)
Hammoud, Ahmad; Stavnes, Mark; Suthar, Jayant; Laghari, Javaid
1995-06-01
Several failures in the electrical wiring systems of many aircraft and space vehicles have been attributed to arc tracking and damaged insulation. In some instances, these failures proved to be very costly as they have led to the loss of many aircraft and imperilment of space missions. Efforts are currently underway to develop lightweight, reliable, and arc track resistant wiring for aerospace applications. In this work, six wiring constructions were evaluated in terms of their breakdown behavior as a function of temperature. These hybrid constructions employed insulation consisting of Kapton, Teflon, and cross-linked Tefzel. The properties investigated included the 400 Hz AC dielectric strength at ambient and 200 C, and the lifetime at high temperature with an applied bias of 40, 60, and 80% of breakdown voltage level. The results obtained are discussed, and conclusions are made concerning the suitability of the wiring constructions investigated for aerospace applications.
In Vivo Ultrasonic Detection of Polyurea Crosslinked Silica Aerogel Implants
Sabri, Firouzeh; Sebelik, Merry E.; Meacham, Ryan; Boughter, John D.; Challis, Mitchell J.; Leventis, Nicholas
2013-01-01
Background Polyurea crosslinked silica aerogels are highly porous, lightweight, and mechanically strong materials with great potential for in vivo applications. Recent in vivo and in vitro studies have demonstrated the biocompatibility of this type of aerogel. The highly porous nature of aerogels allows for exceptional thermal, electric, and acoustic insulating capabilities that can be taken advantage of for non-invasive external imaging techniques. Sound-based detection of implants is a low cost, non-invasive, portable, and rapid technique that is routinely used and readily available in major clinics and hospitals. Methodology In this study the first in vivo ultrasound response of polyurea crosslinked silica aerogel implants was investigated by means of a GE Medical Systems LogiQe diagnostic ultrasound machine with a linear array probe. Aerogel samples were inserted subcutaneously and sub-muscularly in a) fresh animal model and b) cadaveric human model for analysis. For comparison, samples of polydimethylsiloxane (PDMS) were also imaged under similar conditions as the aerogel samples. Conclusion/significance Polyurea crosslinked silica aerogel (X-Si aerogel) implants were easily identified when inserted in either of the regions in both fresh animal model and cadaveric model. The implant dimensions inferred from the images matched the actual size of the implants and no apparent damage was sustained by the X-Si aerogel implants as a result of the ultrasonic imaging process. The aerogel implants demonstrated hyperechoic behavior and significant posterior shadowing. Results obtained were compared with images acquired from the PDMS implants inserted at the same location. PMID:23799093
In vivo ultrasonic detection of polyurea crosslinked silica aerogel implants.
Sabri, Firouzeh; Sebelik, Merry E; Meacham, Ryan; Boughter, John D; Challis, Mitchell J; Leventis, Nicholas
2013-01-01
Polyurea crosslinked silica aerogels are highly porous, lightweight, and mechanically strong materials with great potential for in vivo applications. Recent in vivo and in vitro studies have demonstrated the biocompatibility of this type of aerogel. The highly porous nature of aerogels allows for exceptional thermal, electric, and acoustic insulating capabilities that can be taken advantage of for non-invasive external imaging techniques. Sound-based detection of implants is a low cost, non-invasive, portable, and rapid technique that is routinely used and readily available in major clinics and hospitals. In this study the first in vivo ultrasound response of polyurea crosslinked silica aerogel implants was investigated by means of a GE Medical Systems LogiQe diagnostic ultrasound machine with a linear array probe. Aerogel samples were inserted subcutaneously and sub-muscularly in a) fresh animal model and b) cadaveric human model for analysis. For comparison, samples of polydimethylsiloxane (PDMS) were also imaged under similar conditions as the aerogel samples. Polyurea crosslinked silica aerogel (X-Si aerogel) implants were easily identified when inserted in either of the regions in both fresh animal model and cadaveric model. The implant dimensions inferred from the images matched the actual size of the implants and no apparent damage was sustained by the X-Si aerogel implants as a result of the ultrasonic imaging process. The aerogel implants demonstrated hyperechoic behavior and significant posterior shadowing. Results obtained were compared with images acquired from the PDMS implants inserted at the same location.
Evaluation of fatigue crack behavior in electron beam irradiated polyethylene pipes
NASA Astrophysics Data System (ADS)
Pokharel, Pashupati; Jian, Wei; Choi, Sunwoong
2016-09-01
A cracked round bar (CRB) fatigue test was employed to determine the slow crack growth (SCG) behavior of samples from high density polyethylene (HDPE) pipes using PE4710 resin. The structure property relationships of fatigue failure of polyethylene CRB specimens which have undergone various degree of electron beam (EB) irradiation were investigated by observing fatigue failure strength and the corresponding fracture surface morphology. Tensile test of these HDPE specimens showed improvements in modulus and yield strength while the failure strain decreased with increasing EB irradiation. The CRB fatigue test of HDPE pipe showed remarkable effect of EB irradiation on number of cycles to failure. The slopes of the stress-cycles to failure curve were similar for 0-100 kGy; however, significantly higher slope was observed for 500 kGy EB irradiated pipe. Also, the cycle to fatigue failure was seen to decrease as with EB irradiation in the high stress range, ∆σ=(16 MPa to 10.8 MPa); however, 500 kGy EB irradiated samples showed longer cycles to failure than the un-irradiated specimens at the stress range below 9.9 MPa and the corresponding initial stress intensity factor (∆KI,0)=0.712 MPa m1/2. The fracture surface morphology indicated that the cross-linked network in 500 kGy EB irradiated PE pipe can endure low dynamic load more effectively than the parent pipe.
End-Group Effects on the Properties of PEG-co-PGA Hydrogels
Bencherif, Sidi A.; Srinivasan, Abiraman; Sheehan, Jeffrey A.; Walker, Lynn M.; Gayathri, Chakicherla; Gil, Roberto; Hollinger, Jeffrey O.; Matyjaszewski, Krzysztof; Washburn, Newell R.
2009-01-01
A series of resorbable poly(ethylene glycol)-co-poly(glycolic acid) macromonomers have been synthesized with the chemistries from three different photopolymerizable end-groups (acrylates, methacrylates, and urethane methacrylates). The aim of the study is to examine the effects of the chemistry of the cross-linker group on the properties of photocross-linkable hydrogels. PEG-co-PGA (4KG5) hydrogels were prepared by photopolymerization with high vinyl group conversion as confirmed by 1H NMR spectroscopy using DOSY 1D pulse sequence. Our study reveals that the nature of end-groups in a moderately amphiphilic polymer can adjust the distribution and size of the micellar configuration in water leading to changes in the macroscopic structure of hydrogels. By varying the chemistry of the cross-linker group (diacrylates; DA, dimethacrylates; DM, and urethane dimethacrylates; UDM), we determined that the hydrophobocity of a single core polymer consisting of poly(glycolic acid) could be fine-tuned leading to significant variations in the mechanical, swelling, and degradation properties of the gels. In addition, the effects of cross-linker chemistry on cytotoxicity and proliferation were examined. Cytotoxicity assays showed that all the three types of hydrogels (4KG5 DA, DM, and UDM) were biocompatible and the introduction of RGD ligand enhanced cell adhesion. However, differences in gel properties and stability differentially affected the spreading and proliferation of myoblast C2C12 cells. PMID:19328754
Zhang, Chengfeng; Liu, Ziyuan; Wang, Haiye; Feng, Xiaofeng; He, Chunju
2017-07-01
A unique l-cysteine conjugated antifouling amphiphilic conetwork (APCN) is synthesized through end-crosslinking of well-defined triblock copolymers poly(allyl methacrylate)-b-poly(ethylene glycol)-b-poly(allyl methacrylate) via a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and thiol-ene "click" chemistry. The synthesized poly(ethylene glycol) macro-RAFT agent initiates the polymerization of allyl methacrylate in a controlled manner. The vinyl pendant groups of the precursor partially conjugate with l-cysteine and the rest fully crosslink with mercaptopropyl-containing siloxane via thiol-ene click chemistry under UV irradiation into APCNs, which show distinguished properties, that is, excellent biocompatibility, more than 39.6% water content, 101 barrers oxygen permeability, optimized mechanical properties, and more than 93% visible light transmittance. What's more, the resultant APCNs exhibit eminent resistance to protein adsorption, where the bovine serum albumin and lysozyme adsorption are decreased to 12 and 21 µg cm -2 , respectively. The outstanding properties of APCNs depend on the RAFT controlled method, which precisely designs the hydrophilic/hydrophobic segments and eventually greatly improves the crosslinking efficiency and homogeneity. Meantime, the l-cysteine monolayer can effectively reduce the surface hydrophobicity and prevent protein adsorption, which exhibits the viability for antifouling surface over and under ophthalmic devices, suggesting a promising soft contact lens. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Oral, Ebru; Ghali, Bassem W; Muratoglu, Orhun K
2011-04-01
Radiation crosslinking of ultrahigh molecular weight polyethylene (UHMWPE) has been used to decrease the wear of joint implant bearing surfaces. While radiation crosslinking has been successful in decreasing femoral head penetration into UHMWPE acetabular liners in vivo, postirradiation thermal treatment of the polymer is required to ensure the oxidative stability of joint implants in the long term. Two types of thermal treatment have been used: (i) annealing below the melting point preserves the mechanical properties but the residual free radicals trapped in the crystalline regions are not completely eliminated, leading to oxidation in the long-term and (ii) annealing above the melting point (melting) eliminates the free radicals but leads to a decrease in mechanical properties through loss of crystallinity during the melting process. In this study, we hypothesized that free radicals could be reduced by annealing below the melting point under pressure effectively without melting due to the elevation of the melting point. By avoiding the complete melting of UHMWPE, mechanical properties would be preserved. Our hypothesis tested positive in that we found the radiation-induced free radicals to be markedly reduced (below the detection limit of state-of-the-art electron spin resonance) by thermal annealing under pressure in radiation crosslinked virgin UHMWPE and UHMWPE/vitamin-E blends without loss of mechanical properties. Copyright © 2011 Wiley Periodicals, Inc.
Fung, Mitchell; Bowsher, John G; Van Citters, Douglas W
2018-06-01
Ultra-high molecular weight polyethylene (UHMWPE) is the current gold standard for bearing materials used in total joint arthroplasty. High-dose radiation is commonly used to crosslink UHMWPE, thereby improving its wear resistance. A subsequent remelting step eliminates trapped residual free radicals to promote oxidative stability on the shelf, and to prevent material degradation over the long term. Assessment of clinically retrieved, highly crosslinked UHMWPE devices shows signs of unanticipated oxidation occurring in vivo, despite the absence of free radicals prior to implantation. These findings warrant further investigation into possible factors impacting this phenomenon along with its clinical implications. The overall objective of this work is to quantify the influence of irradiation dose and source on UHMWPE's oxidative stability, along with the effects of oxidation on the ultimate mechanical properties, including strength, ductility, and toughness. The results showed a strong positive correlation between maximum oxidation and initial transvinylene content. Critical oxidation levels in the context of mechanical property loss were determined for e-beam and gamma treatments at various radiation doses. Further, it was shown that critical oxidation was more dependent on radiation dose and less dependent on source. If in vivo oxidation persists in these devices, this can potentially lead to mechanical failure (e.g. fatigue damage) as observed in terminally gamma-sterilized devices. Copyright © 2018 Elsevier Ltd. All rights reserved.
The effects of cross-linked thermo-responsive PNIPAAm-based hydrogel injection on retinal function.
Turturro, Sanja B; Guthrie, Micah J; Appel, Alyssa A; Drapala, Pawel W; Brey, Eric M; Pérez-Luna, Victor H; Mieler, William F; Kang-Mieler, Jennifer J
2011-05-01
There is significant interest in biomaterials that provide sustained release of therapeutic molecules to the retina. Poly(N-isopropylacrylamide) (PNIPAAm)-based materials have received significant attention as injectable drug delivery platforms due to PNIPAAm's thermo-responsive properties at approximately 32 °C. While the drug delivery properties of PNIPAAm materials have been studied extensively, there is a need to evaluate the safety effects of hydrogel injection on retinal function. The purpose of this study was to examine the effect of poly(ethylene glycol) diacrylate (PEG-DA) crosslinked PNIPAAm hydrogel injection on retinal function. Utilizing scanning laser ophthalmoscopy (SLO), optical coherent tomography (OCT), and electroretinography (ERG), retinal function was assessed following hydrogel injection. In region near the hydrogel, there was a significant decrease in arterial and venous diameters (∼4%) and an increase in venous blood velocity (∼8%) 1 week post-injection. Retinal thickness decreased (∼6%) at 1 week and the maximum a- and b-wave amplitudes of ERG decreased (∼15%). All data returned to baseline values after week 1. These data suggest that the injection of PEG-DA crosslinked PNIPAAm hydrogel results in a small transient effect on retinal function without any long-term effects. These results further support the potential of PNIPAAm-based materials as an ocular drug delivery platform. Copyright © 2011 Elsevier Ltd. All rights reserved.
Wang, Zongjie; Abdulla, Raafa; Parker, Benjamin; Samanipour, Roya; Ghosh, Sanjoy; Kim, Keekyoung
2015-12-22
Bioprinting is a rapidly developing technique for biofabrication. Because of its high resolution and the ability to print living cells, bioprinting has been widely used in artificial tissue and organ generation as well as microscale living cell deposition. In this paper, we present a low-cost stereolithography-based bioprinting system that uses visible light crosslinkable bioinks. This low-cost stereolithography system was built around a commercial projector with a simple water filter to prevent harmful infrared radiation from the projector. The visible light crosslinking was achieved by using a mixture of polyethylene glycol diacrylate (PEGDA) and gelatin methacrylate (GelMA) hydrogel with eosin Y based photoinitiator. Three different concentrations of hydrogel mixtures (10% PEG, 5% PEG + 5% GelMA, and 2.5% PEG + 7.5% GelMA, all w/v) were studied with the presented systems. The mechanical properties and microstructure of the developed bioink were measured and discussed in detail. Several cell-free hydrogel patterns were generated to demonstrate the resolution of the solution. Experimental results with NIH 3T3 fibroblast cells show that this system can produce a highly vertical 3D structure with 50 μm resolution and 85% cell viability for at least five days. The developed system provides a low-cost visible light stereolithography solution and has the potential to be widely used in tissue engineering and bioengineering for microscale cell patterning.
Catalytic Hydroxylation of Polyethylenes
2017-01-01
Polyolefins account for 60% of global plastic consumption, but many potential applications of polyolefins require that their properties, such as compatibility with polar polymers, adhesion, gas permeability, and surface wetting, be improved. A strategy to overcome these deficiencies would involve the introduction of polar functionalities onto the polymer chain. Here, we describe the Ni-catalyzed hydroxylation of polyethylenes (LDPE, HDPE, and LLDPE) in the presence of mCPBA as an oxidant. Studies with cycloalkanes and pure, long-chain alkanes were conducted to assess precisely the selectivity of the reaction and the degree to which potential C–C bond cleavage of a radical intermediate occurs. Among the nickel catalysts we tested, [Ni(Me4Phen)3](BPh4)2 (Me4Phen = 3,4,7,8,-tetramethyl-1,10-phenanthroline) reacted with the highest turnover number (TON) for hydroxylation of cyclohexane and the highest selectivity for the formation of cyclohexanol over cyclohexanone (TON, 5560; cyclohexanol/(cyclohexanone + ε-caprolactone) ratio, 10.5). The oxidation of n-octadecane occurred at the secondary C–H bonds with 15.5:1 selectivity for formation of an alcohol over a ketone and 660 TON. Consistent with these data, the hydroxylation of various polyethylene materials by the combination of [Ni(Me4Phen)3](BPh4)2 and mCPBA led to the introduction of 2.0 to 5.5 functional groups (alcohol, ketone, alkyl chloride) per 100 monomer units with up to 88% selectivity for formation of alcohols over ketones or chloride. In contrast to more classical radical functionalizations of polyethylene, this catalytic process occurred without significant modification of the molecular weight of the polymer that would result from chain cleavage or cross-linking. Thus, the resulting materials are new compositions in which hydroxyl groups are located along the main chain of commercial, high molecular weight LDPE, HDPE, and LLDPE materials. These hydroxylated polyethylenes have improved wetting properties and serve as macroinitiators to synthesize graft polycaprolactones that compatibilize polyethylene–polycaprolactone blends. PMID:28852704
Design of an injectable synthetic and biodegradable surgical biomaterial
Zawaneh, Peter N.; Singh, Sunil P.; Padera, Robert F.; Henderson, Peter W.; Spector, Jason A.; Putnam, David
2010-01-01
We report the design of an injectable synthetic and biodegradable polymeric biomaterial comprised of polyethylene glycol and a polycarbonate of dihydroxyacetone (MPEG-pDHA). MPEG-pDHA is a thixotropic physically cross-linked hydrogel, displays rapid chain relaxation, is easily extruded through narrow-gauge needles, biodegrades into inert products, and is well tolerated by soft tissues. We demonstrate the clinical utility of MPEG-pDHA in the prevention of seroma, a common postoperative complication following ablative and reconstructive surgeries, in an animal model of radical breast mastectomy. This polymer holds significant promise for clinical applicability in a host of surgical procedures ranging from cosmetic surgery to cancer resection. PMID:20534478
Irreversible, direct bonding of nanoporous polymer membranes to PDMS or glass microdevices.
Aran, Kiana; Sasso, Lawrence A; Kamdar, Neal; Zahn, Jeffrey D
2010-03-07
A method for integrating porous polymer membranes such as polycarbonate, polyethersulfone and polyethylene terephthalate to microfluidic devices is described. The use of 3-aminopropyltriethoxysilane as a chemical crosslinking agent was extended to integrate membranes with PDMS and glass microfluidic channels. A strong, irreversible bond between the membranes and microfluidic structure was achieved. The bonding strength in the APTES treated devices was significantly greater than in devices fabricated using either a PDMS "glue" or two-part epoxy bonding method. Evaluation of a filtering microdevice and the pore structure via SEM indicates the APTES conjugation does not significantly alter the membrane transport function and pore morphology.
Radiation processing and market economy
NASA Astrophysics Data System (ADS)
Zagórski, Z. P.
1998-06-01
In the system of totalitarian economy, regulated by bureaucracy, the real value of equipment, materials and services is almost completely unknown, what makes impossible the comparison of different technologies, eliminates competition, disturbs research and development. With introduction of market economy in Central and Eastern Europe, the radiation processing has lost doubtful support, becoming an independent business, subject to laws of free market economy. Only the most valuable objects of processing have survived that test. At the top of the list are: radiation sterilization of medical equipment and radiation induced crosslinking of polymers, polyethylene in particular. New elements of competition has entered the scene, as well as questions of international regulations and standards have appeared.
The effect of bearing type on the outcome of total hip arthroplasty.
Peters, Rinne M; Van Steenbergen, Liza N; Stevens, Martin; Rijk, Paul C; Bulstra, Sjoerd K; Zijlstra, Wierd P
2018-04-01
Background and purpose - Alternative bearing surfaces such as ceramics and highly crosslinked polyethylene (HXLPE) were developed in order to further improve implant performance of total hip arthroplasties (THAs). Whether these alternative bearing surfaces result in increased longevity is subject to debate. Patients and methods - Using the Dutch Arthroplasty Register (LROI), we identified all patients with a primary, non-metal-on-metal THA implanted in the Netherlands in the period 2007-2016 (n = 209,912). Cumulative incidence of revision was calculated to determine differences in survivorship of THAs according to bearing type: metal-on-polyethylene (MoPE), metal-on-HXLPE (MoHXLPE), ceramic-on-polyethylene (CoPE), ceramic-on-HXLPE (CoHXLPE), ceramic-on-ceramic (CoC), and oxidized-zirconium-on-(HXL)polyethylene (Ox(HXL)PE). Multivariable Cox proportional hazard regression ratios (HRs) were used for comparisons. Results - After adjustment for confounders, CoHXLPE, CoC, and Ox(HXL)PE resulted in a statistically significantly lower risk of revision compared with MoPE after 9 years follow-up (HR =0.8-0.9 respectively, compared with HR =1.0). For small (22-28 mm) femoral head THAs, lower revision rates were found for CoPE and CoHXLPE (HR =0.9). In the 36 mm femoral head subgroup, CoC-bearing THAs had a lower HR compared with MoHXLPE (HR =0.7 versus 1.0). Crude revision rates in young patients (< 60 years) for CoHXLPE, CoC, and Ox(HXL)PE (HR =0.7) were lower than MoPE (HR =1.0). However, after adjustment for case mix and confounders these differences were not statistically significant. Interpretation - We found a mid-term lower risk of revision for CoHXLPE, CoC, and Ox(HXL)PE bearings compared with traditional MoPE-bearing surfaces.
Pezzotti, Giuseppe; Kumakura, Tsuyoshi; Yamada, Kiyotaka; Tateiwa, Toshiyuki; Puppulin, Leonardo; Zhu, Wenliang; Yamamoto, Kengo
2007-01-01
Confocal spectroscopic techniques are applied to selected Raman bands to study the microscopic features of acetabular cups made of ultra-high molecular weight polyethylene (UHMWPE) before and after implantation in vivo. The micrometric lateral resolution of a laser beam focused on the polymeric surface (or subsurface) enables a highly resolved visualization of 2-D conformational population patterns, including crystalline, amorphous, orthorhombic phase fractions, and oxidation index. An optimized confocal probe configuration, aided by a computational deconvolution of the optical probe, allows minimization of the probe size along the in-depth direction and a nondestructive evaluation of microstructural properties along the material subsurface. Computational deconvolution is also attempted, based on an experimental assessment of the probe response function of the polyethylene Raman spectrum, according to a defocusing technique. A statistical set of high-resolution microstructural data are collected on a fully 3-D level on gamma-ray irradiated UHMWPE acetabular cups both as-received from the maker and after retrieval from a human body. Microstructural properties reveal significant gradients along the immediate material subsurface and distinct differences are found due to the loading history in vivo, which cannot be revealed by conventional optical spectroscopy. The applicability of the confocal spectroscopic technique is valid beyond the particular retrieval cases examined in this study, and can be easily extended to evaluate in-vitro tested components or to quality control of new polyethylene brands. Confocal Raman spectroscopy may also contribute to rationalize the complex effects of gamma-ray irradiation on the surface of medical grade UHMWPE for total joint replacement and, ultimately, to predict their actual lifetime in vivo.
Photocurable poly(ethylene glycol) as a bioink for the inkjet 3D pharming of hydrophobic drugs.
Acosta-Vélez, Giovanny F; Zhu, Timothy Z; Linsley, Chase S; Wu, Benjamin M
2018-04-26
Binder jetting and material extrusion are the two most common additive manufacturing techniques used to create pharmaceutical tablets. However, their versatility is limited since the powder component is present throughout the dosage forms fabricated by binder jet 3D printing and material extrusion 3D printing requires high operating temperatures. Conversely, material jetting allows for compositional control at a voxel level and can dispense material at room temperature. Unfortunately, there are a limited number of materials that are both printable and biocompatible. Therefore, the aim of this study was to engineer photocurable bioinks that are suitable for hydrophobic active pharmaceutical ingredients and have rapid gelation times upon visible light exposure. The resulting bioinks were comprised of poly(ethylene glycol) diacrylate (250 Da) as the crosslinkable monomer, Eosin Y as the photoinitiator, and methoxide-poly(ethylene glycol)-amine as the coinitiator. Additionally, poly(ethylene glycol) (200 Da) was added as a plasticizer to modulate the drug release profiles, and Naproxen was used as the model drug due to its high hydrophobicity. Various bioink formulations were dispensed into the bottom half of blank preform tablets - made via direct compression - using a piezoelectric nozzle, photopolymerized, and capped with the top half of the preform tablet to complete the pharmaceutical dosage form. Results from the release studies showed that drug release can be modulated by both the percent of poly(ethylene glycol) diacrylate in the formulation and the light exposure time used to cure the bioinks. These bioinks have the potential to expand the library of materials available for creating pharmaceutical tablets via inkjet printing with personalized drug dosages. Copyright © 2018 Elsevier B.V. All rights reserved.
Li, Xian; Li, Hao; Yi, Wei; Chen, Jianyu; Liang, Biling
2013-01-01
Purpose To research the acid-triggered core cross-linked folate-poly(ethylene glycol)-b-poly[N-(N′,N′-diisopropylaminoethyl) glutamine] (folated-PEG-P[GA-DIP]) amphiphilic block copolymer for targeted drug delivery and magnetic resonance imaging (MRI) in liver cancer cells. Methods As an appropriate receptor of protons, the N,N-diisopropyl tertiary amine group (DIP) was chosen to conjugate with the side carboxyl groups of poly(ethylene glycol)-b-poly (L-glutamic acid) to obtain PEG-P(GA-DIP) amphiphilic block copolymers. By ultrasonic emulsification, PEG-P(GA-DIP) could be self-assembled to form nanosized micelles loading doxorubicin (DOX) and superparamagnetic iron oxide nanoparticles (SPIONs) in aqueous solution. When PEG-P(GA-DIP) nanomicelles were combined with folic acid, the targeted effect of folated-PEG-P(GA-DIP) nanomicelles was evident in the fluorescence and MRI results. Results To further increase the loading efficiency and the cell-uptake of encapsulated drugs (DOX and SPIONs), DIP (pKa≈6.3) groups were linked with ~50% of the side carboxyl groups of poly(L-glutamic acid) (PGA), to generate the core cross-linking under neutral or weakly acidic conditions. Under the acidic condition (eg, endosome/lysosome), the carboxyl groups were neutralized to facilitate disassembly of the P(GA-DIP) blocks’ cross-linking, for duly accelerating the encapsulated drug release. Combined with the tumor-targeting effect of folic acid, specific drug delivery to the liver cancer cells and MRI diagnosis of these cells were greatly enhanced. Conclusion Acid-triggered and folate-decorated nanomicelles encapsulating SPIONs and DOX, facilitate the targeted MRI diagnosis and therapeutic effects in tumors. PMID:23976852
Abolmaali, Samira Sadat; Tamaddon, Ali; Yousefi, Gholamhossein; Javidnia, Katayoun; Dinarvand, Rasoul
2014-01-01
A functional polycation nanonetwork was developed for delivery of water soluble chemotherapeutic agents. The complexes of polyethyleneimine grafted methoxy polyethylene glycol (PEI-g-mPEG) and Zn(2+) were utilized as the micellar template for cross-linking with dithiodipropionic acid, followed by an acidic pH dialysis to remove the metal ion from the micellar template. The synthesis method was optimized according to pH, the molar ratio of Zn(2+), and the cross-link ratio. The atomic force microscopy showed soft, discrete, and uniform nano-networks. They were sensitive to the simulated reductive environment as determined by Ellman's assay. They showed few positive ζ potential and an average hydrodynamic diameter of 162±10 nm, which decreased to 49±11 nm upon dehydration. The ionic character of the nano-networks allowed the achievement of a higher-loading capacity of methotrexate (MTX), approximately 57% weight per weight, depending on the cross-link and the drug feed ratios. The nano-networks actively loaded with MTX presented some suitable properties, such as the hydrodynamic size of 117±16 nm, polydispersity index of 0.22, and a prolonged swelling-controlled release profile over 24 hours that boosted following reductive activation of the nanonetwork biodegradation. Unlike the PEI ionomer, the nano-networks provided an acceptable cytotoxicity profile. The drug-loaded nano-networks exhibited more specific cytotoxicity against human hepatocellular carcinoma cells if compared to free MTX at concentrations above 1 μM. The enhanced antitumor activity in vitro might be attributed to endocytic entry of MTX-loaded nano-networks that was found in the epifluorescence microscopy experiment for the fluorophore-labeled nano-networks.
Abolmaali, Samira Sadat; Tamaddon, Ali; Yousefi, Gholamhossein; Javidnia, Katayoun; Dinarvand, Rasoul
2014-01-01
A functional polycation nanonetwork was developed for delivery of water soluble chemotherapeutic agents. The complexes of polyethyleneimine grafted methoxy polyethylene glycol (PEI-g-mPEG) and Zn2+ were utilized as the micellar template for cross-linking with dithiodipropionic acid, followed by an acidic pH dialysis to remove the metal ion from the micellar template. The synthesis method was optimized according to pH, the molar ratio of Zn2+, and the cross-link ratio. The atomic force microscopy showed soft, discrete, and uniform nano-networks. They were sensitive to the simulated reductive environment as determined by Ellman’s assay. They showed few positive ζ potential and an average hydrodynamic diameter of 162±10 nm, which decreased to 49±11 nm upon dehydration. The ionic character of the nano-networks allowed the achievement of a higher-loading capacity of methotrexate (MTX), approximately 57% weight per weight, depending on the cross-link and the drug feed ratios. The nano-networks actively loaded with MTX presented some suitable properties, such as the hydrodynamic size of 117±16 nm, polydispersity index of 0.22, and a prolonged swelling-controlled release profile over 24 hours that boosted following reductive activation of the nanonetwork biodegradation. Unlike the PEI ionomer, the nano-networks provided an acceptable cytotoxicity profile. The drug-loaded nano-networks exhibited more specific cytotoxicity against human hepatocellular carcinoma cells if compared to free MTX at concentrations above 1 μM. The enhanced antitumor activity in vitro might be attributed to endocytic entry of MTX-loaded nano-networks that was found in the epifluorescence microscopy experiment for the fluorophore-labeled nano-networks. PMID:24944513
Creating poly(ethylene glycol) film on the surface of NiTi alloy by gamma irradiation
NASA Astrophysics Data System (ADS)
Yu, Hongyan; Yan, Jin; Ma, Huiling; Zeng, Xinmiao; Liu, Yang; Zhao, Xinqing
2015-07-01
NiTi alloy has been extensively utilized as biomaterials owing to its unique shape memory effect, superelasticity and biocompatibility. However, concern with the toxic and allergic responses of nickel potentially releasing from implants stimulated lots of researches of modification on NiTi alloy surface. Creating chemical bond attachment of bioorganic film on NiTi alloy surface could effectively inhibit Ni releasing and obtain bioactive functions for further application. In this work, to get a bioorganic surface, NiTi alloy was modified with poly(ethylene glycol) (PEG) film by gamma ray induced grafting or crosslinking. X-ray diffraction (XRD) spectrum, water contact angle geometer and X-ray photoelectron spectroscopy (XPS) techniques were used to characterize the NiTi surface. The results indicated that PEG was covalent bonded on NiTi alloy surface. Fluorescence microscope (FM) images for morphology of 1 day osteoblast culture on the PEG coated NiTi surface showed that PEG could improve cell proliferation on NiTi surface. Our work offers a way to introduce a bioorganic metal surface by gamma irradiation.
Soil-release behaviour of polyester fabrics after chemical modification with polyethylene glycol
NASA Astrophysics Data System (ADS)
Miranda, T. M. R.; Santos, J.; Soares, G. M. B.
2017-10-01
The fibres cleanability depends, among other characteristics, on their hydrophilicity. Hydrophilic fibres are easy-wash materials but hydrophobic fibres are difficult to clean due to their higher water-repellent surfaces. This type of surfaces, like polyester (PET), produce an accumulation of electrostatic charges, which favors adsorption and retention of dirt. Thus, the polyester soil-release properties can be increased by finishing processes that improve fiber hydrophilicity. In present study, PET fabric modification was described by using poly(ethylene glycol) (PEG) and N,N´-dimethylol-4,5-dihydroxyethylene urea (DMDHEU) chemically modified resin. Briefly, the modification process was carried out in two steps, one to hydrolyse the polyester and create hydroxyl and carboxylic acid groups on the surface and other to crosslink the PEG chains. The resulting materials were characterized by contact angle, DSC and FTIR-ATR methods. Additionally, the soil release behavior and the mechanical properties of modified PET were evaluated. For the best process conditions, the treated PET presented 0° contact angle, grade 5 stain release and acceptable mechanical performance.
Alkschbirs, Melissa I; Bizotto, Vanessa C; de Oliveira, Marcelo G; Sabadini, Edvaldo
2004-12-21
The presence of very small amounts (ppm) of high-MW polymers in solution produces high levels of drag reduction in a turbulent flow. This phenomenon, often termed as the Toms effect, is highly dependent not only on MW, but also on the flexibility of the macromolecular chain. The Toms effect can be studied through the images of the structures produced after the drop impact against shallow solution surfaces. The splash structures composed of crown, cavity, and Rayleigh jet are highly dependent on the elongational properties of the solution. This work presents the effects of Congo red on the drag reduction properties of poly(ethylene oxide) in aqueous solutions through the analysis of splash structures. Results obtained in this analysis indicate that Congo red molecules act as physical cross-linking agents, decreasing the polymer elasticity and its drag reduction capacity. It was observed that the maximum height of the Rayleigh jet can be used as a sensitive parameter to the complexation between the dye and the polymer molecules.
Ganji, Yasaman; Kasra, Mehran; Salahshour Kordestani, Soheila; Bagheri Hariri, Mohiedin
2014-09-01
Gold nanotubes/nanowires (GNT/NW) were synthesized by using the template-assisted electrodeposition technique and mixed with castor oil-polyethylene glycol based polyurethane (PU) to fabricate porous composite scaffolds for biomedical application. 100 and 50 ppm of GNT/NW were used to synthesize composites. The composite scaffolds were characterized by Fourier transform infrared spectroscopy, dynamic mechanical thermal analysis, differential scanning calorimetry, and scanning electron microscopy. Cell attachment on polyurethane-GNT/NW composites was investigated using fat-derived mesenchymal stem cells. Addition of 50 or 100 ppm GNT/NW had significant effects on thermal, mechanical, and cell attachment of polyurethane. Higher crosslink density and better cell attachment and proliferation were observed in polyurethane containing 50 ppm GNT/NW. The results revealed that GNT/NW formed hydrogen bonding with the polyurethane matrix and improved the thermomechanical properties of nanocomposites. Compared with pure PU, better cellular attachment on polyurethane-GNT/NW composites was observed resulting from the improved surface properties of composites. Copyright © 2014 Elsevier B.V. All rights reserved.
Deterred drug abuse using superabsorbent polymers.
Mastropietro, David J; Muppalaneni, Srinath; Omidian, Hossein
2016-11-01
This study aimed to determine whether selected superabsorbent polymers (SAPs) could be used as a suitable alternative to thwart extraction, filtration, and syringeability attempts for abuse. Many abuse-deterrent formulations (ADFs) rely on high molecular weight polymers such as poly(ethylene oxide) to provide crush and extraction resistance. However, these polymers suffer from slow dissolution kinetics, and are susceptible to a variety of abuse conditions. Several commercially available SAPs were evaluated for swelling behavior in extraction solvents, and tableting properties. Post-compaction abuse properties were evaluated by recoverable volume and syringeability after solvent extraction. Drug release and percent drug extraction were conducted using tramadol HCl as a model drug. Certain SAPs had the ability to rapidly imbibe solvent and effectively stop extraction processes in a variety of solvents, including water and water/alcohol mixtures. Tablets containing SAP and drug showed no effect on drug release in vitro. SAPs possess adequate properties for tableting, and maintain their high and fast swelling properties after compaction. The fast and extensive interactions of SAPs with aqueous medium are a major advantage over non-crosslinked high molecular weight viscosifying agents such as poly(ethylene oxide).
Development of an iron chelating polyethylene film for active packaging applications.
Tian, Fang; Decker, Eric A; Goddard, Julie M
2012-02-29
Metal-promoted oxidation reactions are a major cause of food quality deterioration. Active packaging offers novel approaches to controlling such oxidation for the purpose of extending shelf life. Herein, we report modification of the surface of polyethylene (PE) films to possess metal chelating activity. Metal chelating carboxylic acids were introduced to the film surface using cross-linking agents [polyethylenimine (PEI) or ethylenediamine (ED)] to increase the number of available carboxylic acids. ATR-FTIR, contact angle, dye assay, and iron chelating assay were used to characterize changes in surface chemistry after each functionalization step. The chelator poly(acrylic acid) (PAA) was attached to the surface at a density of 9.12 ± 0.71 nmol carboxyl groups/cm², and exhibited an iron chelating activity. The results indicate that PAA-modified PE films might have a higher affinity to Fe³⁺ than Fe²⁺ with the optimum binding pH at 5.0. Such inexpensive active packaging materials are promising in food industry for the preservation of liquid and semiliquid food products and have application in heavy metal chelation therapy for biomedical materials as well.
Bolasco, Piergiorgio; Contu, Antonio; Meloni, Patrizia; Vacca, Dorio; Murtas, Stefano
2012-01-01
This report attempts to illustrate the positive impact on the quality of dialysis water produced over a 16-year period through the progressive optimization of technological procedures. Fundamental steps included the following: elimination of polyvinyl chloride (PVC), periodical controls, introduction of stainless steel and/or polyethylene polymer and substitution of single-pass reverse osmosis (SRO) with double-pass reverse osmosis (DRO). Daily overnight automatic thermal disinfection of distribution piping rings represented the final step. A dramatic improvement was observed in 645 water samples obtained from distribution piping. The measures applied resulted in a significant improvement of water quality, featuring levels of colony-forming units per milliliter ranging from 247.4 ± 393.7 in the presence of PVC and SRO to 14.1 ± 28.0 with stainless steel and DRO and 2.8 ± 3.2 with cross-linked polyethylene thermoplastic polymer and DRO (p < 0.01). Dialysis water should be viewed by nephrologists as a medicinal product, and every effort should be made to ensure a high-quality liquid. Copyright © 2012 S. Karger AG, Basel.
NASA Astrophysics Data System (ADS)
Li, Qiaochu; Barret, Devin G.; Messersmith, Phillip B.; Holten-Andersen, Niels
2014-03-01
Polymer-nanoparticle (NP) composites have attracted renewed attention due to enhanced mechanical strength combined with various functionalities, but controlling the interfacial chemistry between NPs and polymer matrix, which is crucial for the composite's mechanical behavior, remains a major challenge. Inspired by the adhesion chemistry of mussel fibers, we investigated a novel approach to incorporate Fe3O4 NPs into hydrogel matrix. A polyethylene glycol polymer is designed with both ends conjugated by catechol groups, which have strong coordination affinity to Fe. The polymer network is crosslinked via coordination bonding at the surface of Fe3O4 NPs, yielding a stiff nanocomposite hydrogel. Due to the reversible nature of coordination bonding, the hydrogel presents self-healing behavior. Oscillatory rheology allows comparative kinetic studies of self-healing driven by catechol bonding at Fe3O4 NP interfaces and by catechol-Fe3+ coordination complexes. Furthermore, the superparamagnetic property of Fe3O4 NP is preserved after gelation, allowing for response to external stimuli. This gelation motif can serve as a versatile platform for tuning functional and mechanical properties for future polymer nanocomposite materials.
Controlled grafting of vinylic monomers on polyolefins: a robust mathematical modeling approach
Saeb, Mohammad Reza; Rezaee, Babak; Shadman, Alireza; Formela, Krzysztof; Ahmadi, Zahed; Hemmati, Farkhondeh; Kermaniyan, Tayebeh Sadat; Mohammadi, Yousef
2017-01-01
Abstract Experimental and mathematical modeling analyses were used for controlling melt free-radical grafting of vinylic monomers on polyolefins and, thereby, reducing the disturbance of undesired cross-linking of polyolefins. Response surface, desirability function, and artificial intelligence methodologies were blended to modeling/optimization of grafting reaction in terms of vinylic monomer content, peroxide initiator concentration, and melt-processing time. An in-house code was developed based on artificial neural network that learns and mimics processing torque and grafting of glycidyl methacrylate (GMA) typical vinylic monomer on high-density polyethylene (HDPE). Application of response surface and desirability function enabled concurrent optimization of processing torque and GMA grafting on HDPE, through which we quantified for the first time competition between parallel reactions taking place during melt processing: (i) desirable grafting of GMA on HDPE; (ii) undesirable cross-linking of HDPE. The proposed robust mathematical modeling approach can precisely learn the behavior of grafting reaction of vinylic monomers on polyolefins and be placed into practice in finding exact operating condition needed for efficient grafting of reactive monomers on polyolefins. PMID:29491797
Controlled grafting of vinylic monomers on polyolefins: a robust mathematical modeling approach.
Saeb, Mohammad Reza; Rezaee, Babak; Shadman, Alireza; Formela, Krzysztof; Ahmadi, Zahed; Hemmati, Farkhondeh; Kermaniyan, Tayebeh Sadat; Mohammadi, Yousef
2017-01-01
Experimental and mathematical modeling analyses were used for controlling melt free-radical grafting of vinylic monomers on polyolefins and, thereby, reducing the disturbance of undesired cross-linking of polyolefins. Response surface, desirability function, and artificial intelligence methodologies were blended to modeling/optimization of grafting reaction in terms of vinylic monomer content, peroxide initiator concentration, and melt-processing time. An in-house code was developed based on artificial neural network that learns and mimics processing torque and grafting of glycidyl methacrylate (GMA) typical vinylic monomer on high-density polyethylene (HDPE). Application of response surface and desirability function enabled concurrent optimization of processing torque and GMA grafting on HDPE, through which we quantified for the first time competition between parallel reactions taking place during melt processing: (i) desirable grafting of GMA on HDPE; (ii) undesirable cross-linking of HDPE. The proposed robust mathematical modeling approach can precisely learn the behavior of grafting reaction of vinylic monomers on polyolefins and be placed into practice in finding exact operating condition needed for efficient grafting of reactive monomers on polyolefins.
Hu, Xiufeng; Wang, Ning; Liu, Lu; Liu, Wenguang
2013-01-01
A hydrogen bonding strengthened hydrogel was prepared by radical copolymerization of poly(ethylene glycol) methacrylated β-cyclodextrin (PEG-β-CD) and 2-vinyl-4,6-diamino-1,3,5-triazine (VDT) monomer. PEG-β-CD served not only as a cross-linker, but also as a built-in solubilizing agent of the hydrophobic drug in the gel. Increasing VDT content resulted in a notable enhancement in the mechanical strengths of hydrogels whose equilibrium water contents could be modulated from 75% to 85% by varying the ratio of PEG-β-CD cross-linker. It was shown that copolymerizing more PEG-β-CDs could load higher amount of ibuprofen (IBU) in the gels and contribute to a slower release rate of IBU. Plasmid DNA could be anchored onto the surface of hydrogels due to the hydrogen bonding between the base pairs and diaminotriazine, thereby mediating efficient reverse gene transfection of luciferase gene in COS-7 cells cultured on the gel surface. The cytocompatible PEG-β-CD-cross-linked PVDT hydrogels with multifunction of drug and gene delivery hold a potential as tissue engineering scaffold.
Formation of Heterogeneous Toroidal-Spiral Particles -- by Drop Sedimentation and Interaction
NASA Astrophysics Data System (ADS)
Liu, Ying; Nitsche, Ludwig; Gemeinhart, Richard; Sharma, Vishal; Szymusiak, Magdalena; Shen, Hao
2013-03-01
We describe self-assembly of polymeric particles, whereby competitive kinetics of viscous sedimentation, diffusion, and cross-linking yield a controllable toroidal-spiral (TS) structure. Precursor polymeric droplets are splashed through the surface of a less dense, miscible solution, after which viscous forces entrain the surrounding bulk solution into the sedimenting polymer drop to form TS channels. The intricate structure forms because low interfacial tension between the two miscible solutions is dominated by viscous forces. The biocompatible polymer, poly(ethylene glycol) diacrylate (PEG-DA), is used to demonstrate the solidification of the TS shapes at various configurational stages by UV-triggered cross-linking. The dimensions of the channels are controlled by Weber number during impact on the surface, and Reynolds number and viscosity ratio during subsequent sedimentation. Within the critical separation distance, interaction of multiple drops generates similar structure with more flexibility. Furthermore, the understanding of multiple drop interaction is essential for mass production of TS particles by using parallel and sequential arrays of drops. This work was supported by NSF CBET Grant CBET-1039531.
NASA Astrophysics Data System (ADS)
Ortiz, A. V.; Teixeira, J. G.; Gomes, M. G.; Oliveira, R. R.; Díaz, F. R. V.; Moura, E. A. B.
2014-08-01
This work evaluates the morphology, mechanical and thermo-mechanical properties of high density polyethylene (HDPE) composites. HDPE reinforced with rice husk ashes (80:20 wt%), HDPE reinforced with clay (97:3 wt%) and HDPE reinforced with both rice husk ashes and clay(77:20:3 wt%) were obtained. The Brazilian bentonite chocolate clay was used in this study. This Brazilian smectitic clay is commonly used to produce nanocomposites. The composites were produced by melting extrusion process and then irradiation was carried out in a 1.5 MeV electron-beam accelerator (room temperature, presence of air). Comparisons using the irradiated and non-irradiated neat polymer, and the irradiated and non-irradiated composites were made. The materials obtained were submitted to tensile, flexural and impact tests. Additionally HDT, SEM and XRD analyses were carried out along with the sol-gel analysis which aimed to assess the cross-linking degree of the irradiated materials. Results showed great improvement in most HDPE properties and a high cross-linking degree of 85% as a result of electron-beam irradiation of the material.
Recycle polymer characterization and adhesion modeling
NASA Astrophysics Data System (ADS)
Holbery, James David
Contaminants from paper product producers that adversely affect fiber yield have been collected from mills located in three North American geographic regions. Samples have been fractionated using a modified solvent extraction process and subsequently quantitatively characterized and it was found that agglomerates were comprised of the following: approximately 30% extractable polymeric material, 25--35% fiber, 12--15% inorganic material, 15% non-extractable high molecular-weight polyethylene or cross-linked polymers, and 2--4% starch residue. Three representative polymers, paraffin, low-molecular weight polyethylene, and a commercial hot-melt adhesive were selected for further analysis to model the attractive and repulsive behavior using Scanning Probe Microscopy in an aqueous cell. Scanning force probes were characterized using an original technique utilizing a nano-indentation apparatus that is non-destructive and is accurate to within 10% for probes with force constants as low as 1 N/m. Surface force measurements were performed between a Poly (Styrene/30% Butyl Methacrylate) sphere and substrates produced from paraffin, polyethylene, and a commercial hot-melt adhesive in solutions ranging in NaF ionic concentrations from 0.001M to 1M. Reasonable theoretical agreement with experimental data has been shown between a combined model applying van der Waals force contributions using the Derjaguin approximation and electrostatic contributions as predicted by a Debye-Huckel linearization of the Poisson-Boltzmann equation utilizing Hamaker constants derived from critical surface energies determined from Zisman and Lifshitz-van der Waals energy approaches. This model has been applied to measured data and indicates the strength of adhesion for the hot-melt to be 0.14 nN while that of paraffin is 1.9 nN and polyethylene 2.8 nN. Paraffin and polyethylene are 13.5 and 20 times greater in attraction than the hot-melt adhesive. Hot-melt adhesive repulsion is predicted to be 220 pN while for paraffin it is 9.1 nN and polyethylene 12.2 nN, a factor of 41 and 55 greater for paraffin and polyethylene, respectively. Decay lengths for repulsion is fit to be 2.3 nm for hotmelt indicating, approximately one-third that of paraffin and polyethylene. Johnson-Kendall-Roberts contact mechanic theory for viscoelastic materials has been applied with reasonable accuracy, particularly in experiments performed in solutions, to model the approach snap-in magnitude and detachment forces between sphere and substrate. Two representative commercial agglomeration formulations have been analyzed to determine the impact on adhesion and detachment forces although at room temperature, no measurable effect was identified.
The electro-mechanical effect from charge dynamics on polymeric insulation lifetime
DOE Office of Scientific and Technical Information (OSTI.GOV)
Alghamdi, H., E-mail: haalghamdi@nu.edu.sa; Faculty of Engineering, Najran University, Najran, P.O.Box 1988; Chen, G.
For polymeric material used as electrical insulation, the presence of space charges could be the consequence of material degradations that are thermally activated but increased by the application of an electric field. The dynamics of space charge, therefore, can be potentially used to characterize the material. In this direction, a new aging model in which parameters have clear physical meanings has been developed and applied to the material to extrapolate the lifetime. The kinetic equation has been established based on charge trapping and detrapping of the injected charge from the electrodes. The local electromechanical energy stored in the region surroundingmore » the trap is able to reduce the trap-depth with a value related to the electric field. At a level where the internal electric field exceeds the detrapping field in the material, an electron can be efficiently detrapped and the released energy from detrapping process can cause a weak bond or chain scission i.e. material degradation. The model has been applied to the electro-thermally aged low density polyethylene film samples, showing well fitted result, as well as interesting relationships between parameter estimates and insulation morphology.« less
He, Hao; Zhang, Qixing; Tu, Ran; Zhao, Luyao; Liu, Jia; Zhang, Yongming
2016-12-15
The dripping behavior of the molten thermoplastic insulation of copper wire, induced by flame spread under overload currents, was investigated for a better understanding of energized electrical wire fires. Three types of sample wire, with the same polyethylene insulation thickness and different core diameters, were used in this study. First, overload current effects on the transient one-dimensional wire temperature profile were predicted using simplified theoretical analysis; the heating process and equilibrium temperature were obtained. Second, experiments on the melting characteristics were conducted in a laboratory environment, including drop formation and frequency, falling speed, and combustion on the steel base. Third, a relationship between molten mass loss and volume variation was proposed to evaluate the dripping time and frequency. A strong current was a prerequisite for the wire dripping behavior and the averaged dripping frequency was found to be proportional to the square of the current based on the theoretical and experimental results. Finally, the influence of dripping behavior on the flame propagation along the energized electrical wire was discussed. The flame width, bright flame height and flame spreading velocity presented different behaviors. Copyright © 2016 Elsevier B.V. All rights reserved.
Suganuma, Y; Dhirani, A-A
2011-04-01
The present study explores a novel apertured microchip conductance detector (AMCD) that is sensitive to dielectric constant. Fashioned on silicon oxide/silicon using optical microlithography, the detector has novel parallel-plate geometry with a top mesh electrode, a middle apertured insulator, and a bottom conducting electrode. This monolithic apertured architecture is planar and may be provided with a thin insulator layer enabling large capacitances, while the top mesh electrode and middle apertured-insulator enable access to regions of the capacitor where electric fields are strong. Hence, the detector is sensitive yet mechanically robust. To test its response, the AMCD was immersed in various solvents, namely water, methanol, acetonitrile, and hexanes. Its response was found to vary in proportion to the solvents' respective dielectric constants. The AMCD was also able to distinguish quantitatively the presence of various molecules in solution, including molecules with chromophores [such as acetylsalicylic acid (ASA)] in methanol and those without chrompohores [such as polyethylene glycol 200 Daltons (PEG200)] in methanol or water. The universal nature of dielectric constant and the microchip detector's sensitivity point to a wide range of potential applications. © 2011 American Institute of Physics
NASA Astrophysics Data System (ADS)
Schmidt, F.
1980-11-01
The components of a superconducting 110 kV ac cable for power ratings or = 2000 MVA were developed. The cable design is of the semiflexible type, with a rigid cryogenic envelope containing a flexible hollow coaxial cable core. The cable core consists of spirally wound Nb-A1 composite wires electrically insulated by high pressure polyethylene tape wrappings. A 35 m long single phase test cable with full load terminals rated at 110 kV and 10 kA was constructed and successfully tested. The results obtained prove the technical feasibility and capability of this cable design.
NASA Astrophysics Data System (ADS)
Jia, Shaojin; Zhang, Zhicheng; Du, Zhiwen; Teng, Renrui; Wang, Zhengzhou
2003-04-01
A dynamic flammability study of flame-retardant compound consisting of HDPE, EPDM and silicon elastomer blended with additives, as wire and cable insulation was made before and after irradiation. The data of RHR, EHC, SEC and the concentration of CO and CO 2 from cone colorimeter shown in the burning process were accessed. By blending silicon elastomer, CO release rate was reduced and the thermal endurance was improved. Oxygen index, mechanical property, morphology of the char formed in dynamical flame and thermal stability were also investigated.
Revision total hip arthoplasty: factors associated with re-revision surgery.
Khatod, Monti; Cafri, Guy; Inacio, Maria C S; Schepps, Alan L; Paxton, Elizabeth W; Bini, Stefano A
2015-03-04
The survivorship of implants after revision total hip arthroplasty and risk factors associated with re-revision are not well defined. We evaluated the re-revision rate with use of the institutional total joint replacement registry. The purpose of this study was to determine patient, implant, and surgeon factors associated with re-revision total hip arthroplasty. A retrospective cohort study was conducted. The total joint replacement registry was used to identify patients who had undergone revision total hip arthroplasty for aseptic reasons from April 1, 2001, to December 31, 2010. The end point of interest was re-revision total hip arthroplasty. Risk factors evaluated for re-revision total hip arthroplasty included: patient risk factors (age, sex, body mass index, race, and general health status), implant risk factors (fixation type, bearing surface, femoral head size, and component replacement), and surgeon risk factors (volume and experience). A multivariable Cox proportional hazards model was used. Six hundred and twenty-nine revision total hip arthroplasties with sixty-three (10%) re-revisions were evaluated. The mean cohort age (and standard deviation) was 57.0 ± 12.4 years, the mean body mass index (and standard deviation) was 29.5 ± 6.1 kg/m(2), and most of the patients were women (64.5%) and white (81.9%) and had an American Society of Anesthesiologists score of <3 (52.9%). The five-year implant survival after revision total hip arthroplasty was 86.8% (95% confidence interval, 83.57% to 90.25%). In adjusted models, age, total number of revision surgical procedures performed by the surgeon, fixation, and bearing surface were associated with the risk of re-revision. For every ten-year increase in patient age, the hazard ratio for re-revision decreases by a factor of 0.72 (95% confidence interval, 0.58 to 0.90). For every five revision surgical procedures performed by a surgeon, the risk of revision decreases by a factor of 0.93 (95% confidence interval, 0.86 to 0.99). At the time of revision, a new or retained cemented femoral implant or all-cemented hip implant increases the risk of revision by a factor of 3.19 (95% confidence interval, 1.22 to 8.38) relative to a retained or new uncemented hip implant. A ceramic on a highly cross-linked polyethylene bearing articulation decreases the hazard relative to metal on highly cross-linked polyethylene by a factor of 0.32 (95% confidence interval, 0.11 to 0.95). Metal on constrained bearing increases the hazard relative to metal on highly cross-linked polyethylene by a factor of 3.32 (95% confidence interval, 1.16 to 9.48). When evaluating patient, implant, and surgical factors at the time of revision total hip arthroplasty, age, surgeon experience, implant fixation, and bearing surfaces had significant impacts on the risk of re-revision. Copyright © 2015 by The Journal of Bone and Joint Surgery, Incorporated.
Wong, James Min-Leong; Liu, Yen-Liang; Graves, Stephen; de Steiger, Richard
2015-11-01
More than 15,000 primary hip resurfacing arthroplasties have been recorded by the Australian Orthopaedic Association National Joint Replacement Registry (AOANJRR) with 884 primary procedures requiring revision for reasons other than infection, a cumulative percent revision rate at 12 years of 11%. However, few studies have reported the survivorship of these revision procedures. (1) What is the cumulative percent rerevision rate for revision procedures for failed hip resurfacings? (2) Is there a difference in rerevision rate among different types of revision or bearing surfaces? The AOANJRR collects data on all primary and revision hip joint arthroplasties performed in Australia and after verification against health department data, checking of unmatched procedures, and subsequent retrieval of unreported procedures is able to obtain an almost complete data set relating to hip arthroplasty in Australia. Revision procedures are linked to the known primary hip arthroplasty. There were 15,360 primary resurfacing hip arthroplasties recorded of which 884 had undergone revision and this was the cohort available to study. The types of revisions were acetabular only, femoral only, or revision of both acetabular and femoral components. With the exception of the acetabular-only revisions, all revisions converted hip resurfacing arthroplasties to conventional (stemmed) total hip arthroplasties (THAs). All initial revisions for infection were excluded. The survivorship of the different types of revisions and that of the different bearing surfaces used were estimated using the Kaplan-Meier method and compared using Cox proportional hazard models. Cumulative percent revision was calculated by determining the complement of the Kaplan-Meier survivorship function at that time multiplied by 100. Of the 884 revisions recorded, 102 underwent further revision, a cumulative percent rerevision at 10 years of 26% (95% confidence interval, 19.6-33.5). There was no difference in the rate of rerevision between acetabular revision and combined femoral and acetabular revision (hazard ratio [HR], 1.06 [0.47-2], p = 0.888), femoral revision and combined femoral and acetabular revision (HR, 1.00 [0.65-2], p = 0.987), and acetabular revision and femoral revision (HR, 1.06 [0.47-2], p = 0.893). There was no difference in the rate of rerevision when comparing different bearing surfaces (metal-on-metal versus ceramic-on-ceramic HR, 0.46 [0.16-1.29], p = 0.141; metal-on-metal versus ceramic-on-crosslinked polyethylene HR, 0.51 [0.15-1.76], p = 0.285; metal-on-metal versus metal-on-crosslinked polyethylene HR, 0.62 [0.20-1.89], p = 0.399; and metal-on-metal versus oxinium-on-crosslinked polyethylene HR, 0.53 [0.14-2.05], p = 0.356). Revision of a primary hip resurfacing arthroplasty is associated with a high risk of rerevision. This study may help surgeons guide their patients about the outcomes in the longer term after the first revision of hip resurfacing arthroplasty. Level III, therapeutic study.
Stress-Dependent Voltage Offsets From Polymer Insulators Used in Rock Mechanics and Material Testing
NASA Technical Reports Server (NTRS)
Carlson, G. G.; Dahlgren, Robert; Gray, Amber; Vanderbilt, V. C.; Freund, F.; Johnston, M. J.; Dunson, C.
2013-01-01
Dielectric insulators are used in a variety of laboratory settings when performing experiments in rock mechanics, petrology, and electromagnetic studies of rocks in the fields of geophysics,material science, and civil engineering. These components may be used to electrically isolate geological samples from the experimental equipment, to perform a mechanical compliance function between brittle samples and the loading equipment, to match ultrasonic transducers, or perform other functions. In manyexperimental configurations the insulators bear the full brunt of force applied to the sample but do not need to withstand high voltages, therefore the insulators are often thin sheets of mechanically tough polymers. From an instrument perspective, transduction from various types of mechanical perturbation has beenqualitatively compared for a number of polymers [1, 2] and these error sources are readily apparent duringhigh-impedance measurements if not mitigated. However even when following best practices, a force dependent voltage signal still remains and its behavior is explored in this presentation. In this experimenttwo thin sheets (0.25 mm) of high-density polyethylene (HDPE) were set up in a stack, held alternatelybetween three aluminum bars; this stack was placed on the platen of a 60T capacity hydraulic testingmachine. The surface area, A, over which the force is applied to the PE sheets in this sandwich is roughly 40 square cm, each sheet forming a parallel-plate capacitor having roughly 320 pF [3], assuming therelative dielectric permittivity of PE is approximately 2.3. The outer two aluminum bars were connected to the LO input ofthe electrometer and the central aluminum bar was connected to the HI input of a Keithley model 617 electrometer. Once the stack is mechanically well-seated with no air gaps, the voltage offset is observed tobe a linear function of the baseline voltage for a given change in applied force. For a periodically appliedforce of 66.7 kN the voltage offsets were measured as a function of initial voltage, and these data were fitwith a linear function that was constrained to pass through the origin. The best fit solution had a correlation coefficient of R=0.85 and a slope of approximately -0.0228 volts/volt. The voltage offset when normalizedis demonstrated to be constant -2.28% for both positive and negative polarities over nearly 3 orders ofbaseline voltage magnitude. From this, the voltage-force coefficient is derived to be -0.34 ppm/N. Thiscorrelates well to a first-order parallel plate capacitor model that assumes constant area, and smalldeformation such that the polymer may be mechanically modeled by a spring that obeys Hookes law. Thissimple model predicts that the coefficient of proportionality is a function of Youngs modulus E= 0.8 GPaand surface area of the insulator, theoretically -1EA= -0.31 ppm/N. The outcome of this work is animproved insulator made from ultra-high molecular weight (UHMW) polyethylene and other approachestoward the minimization of and compensation for these experimental artifacts.
Wang, Youyuan; Zhang, Zhanxi; Xiao, Kun
2017-01-01
This paper investigates the morphology, thermal, and electrical properties of LDPE (low-density polyethylene)-based nanocomposites after thermal aging. The FTIR (Fourier transform infrared spectroscopy) spectra results show that thermo-oxidative reactions occur in neat LDPE and LDPE/SiO2 nanocomposites when the aging time is 35 days and in LDPE/MgO nanocomposites when the aging time is 77 days. Specifically, LDPE/MgO nanocomposites delay the appearance of thermo-oxidative reactions, showing anti-thermal aging ability. Furthermore, nanocomposites present lower onset degradation temperature than neat LDPE, showing better thermal stabilization. With regard to the electrical properties, nanocomposites maintain the ability to suppress space charge accumulation after thermal aging. Additionally, in comparison with SiO2 nanocomposites and neat LDPE, the permittivity of LDPE/MgO nanocomposites changes slightly after thermal aging. It is concluded that LDPE/MgO nanocomposites have better insulation properties than neat LDPE after thermal aging, which may be caused by the interface introduced by the nanoparticles. PMID:29023428
Wang, Youyuan; Wang, Can; Zhang, Zhanxi; Xiao, Kun
2017-10-12
This paper investigates the morphology, thermal, and electrical properties of LDPE (low-density polyethylene)-based nanocomposites after thermal aging. The FTIR (Fourier transform infrared spectroscopy) spectra results show that thermo-oxidative reactions occur in neat LDPE and LDPE/SiO₂ nanocomposites when the aging time is 35 days and in LDPE/MgO nanocomposites when the aging time is 77 days. Specifically, LDPE/MgO nanocomposites delay the appearance of thermo-oxidative reactions, showing anti-thermal aging ability. Furthermore, nanocomposites present lower onset degradation temperature than neat LDPE, showing better thermal stabilization. With regard to the electrical properties, nanocomposites maintain the ability to suppress space charge accumulation after thermal aging. Additionally, in comparison with SiO₂ nanocomposites and neat LDPE, the permittivity of LDPE/MgO nanocomposites changes slightly after thermal aging. It is concluded that LDPE/MgO nanocomposites have better insulation properties than neat LDPE after thermal aging, which may be caused by the interface introduced by the nanoparticles.
High temperature homogenization improves impact toughness of vitamin E-diffused, irradiated UHMWPE.
Oral, Ebru; O'Brien, Caitlin; Doshi, Brinda; Muratoglu, Orhun K
2017-06-01
Diffusion of vitamin E into radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is used to increase stability against oxidation of total joint implant components. The dispersion of vitamin E throughout implant preforms has been optimized by a two-step process of doping and homogenization. Both of these steps are performed below the peak melting point of the cross-linked polymer (<140°C) to avoid loss of crystallinity and strength. Recently, it was discovered that the exposure of UHMWPE to elevated temperatures, around 300°C, for a limited amount of time in nitrogen, could improve the toughness without sacrificing wear resistance. We hypothesized that high temperature homogenization of antioxidant-doped, radiation cross-linked UHMWPE could improve its toughness. We found that homogenization at 300°C for 8 h resulted in an increase in the impact toughness (74 kJ/m 2 compared to 67 kJ/m 2 ), the ultimate tensile strength (50 MPa compared to 43 MPa) and elongation at break (271% compared to 236%). The high temperature treatment did not compromise the wear resistance or the oxidative stability as measured by oxidation induction time. In addition, the desired homogeneity was achieved at a much shorter duration (8 h compared to >240 h) by using high temperature homogenization. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 35:1343-1347, 2017. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.
PEG-based degradable networks for drug delivery applications
NASA Astrophysics Data System (ADS)
Ostroha, Jamie L.
The controlled delivery of therapeutic agents by biodegradable hydrogels has become a popular mechanism for drug administration in recent years. Hydrogels are three-dimensional networks of polymer chains held together by crosslinks. Although the changes which the hydrogel undergoes in solution are important to a wide range of experimental studies, they have not been investigated systematically and the factors which influence the degree of swelling have not been adequately described. Hydrogels made of poly(ethylene glycol) (PEG) will generally resist degradation in aqueous conditions, while a hydrogel made from a copolymer of poly(lactic acid) (PLA) and PEG will degrade via hydrolysis of the lactic acid group. This ability to degrade makes these hydrogels promising candidates for controlled release drug delivery systems. The goal of this research was to characterize the swelling and degradation of both degradable and non-degradable gels and to evaluate the release of different drugs from these hydrogels, where the key variable is the molecular weight of the PEG segment. These hydrogels were formed by the addition and subsequent chemically crosslinking of methacrylate end groups. During crosslinking, both PEG and LA-PEG-LA hydrogels of varied PEG molecular weight were loaded with Vitamin B12, Insulin, Haloperidol, and Dextran. It was shown that increasing PEG molecular weight produces a hydrogel with larger pores, thus increasing water uptake and degradation rate. While many environmental factors do not affect the swelling behavior, they do significantly impact the degradation of the hydrogel, and thus the release of incorporated therapeutic agents.
Barkay-Olami, Hilla; Zilberman, Meital
2016-08-01
Use of naturally derived materials for biomedical applications is steadily increasing. Soy protein has advantages over various types of natural proteins employed for biomedical applications due to its low price, nonanimal origin, and relatively long storage time and stability. In the current study, blends of soy protein with other polymers (gelatin, alginate, pectin, polyvinyl alcohol, and polyethylene glycol) were developed and studied. The mechanical tensile properties of dense films were studied in order to select the best secondary polymer for porous three-dimensional structures. The porous soy-gelatin and soy-alginate structures were then studied for physical properties, degradation behavior, and microstructure. The results show that these blends can be assembled into porous three-dimensional structures by combining chemical crosslinking with freeze-drying. The soy-alginate blends are advantageous over soy-gelatin blends, demonstrated better stability, and degradation time along with controlled swelling behavior due to more effective crosslinking and higher water uptake than soy-gelatin blends. Water vapor transmission rate experiments showed that all porous blend structures were in the desired range for burn treatment [2000-2500 g/(m(2) d)] and can be controlled by the crosslinking process. We conclude that these novel porous three-dimensional structures have a high potential for use as scaffolds for tissue engineering, especially for skin regeneration applications. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1109-1120, 2016. © 2015 Wiley Periodicals, Inc.
Efficient barrier for charge injection in polyethylene by silver nanoparticles/plasma polymer stack
DOE Office of Scientific and Technical Information (OSTI.GOV)
Milliere, L.; Makasheva, K., E-mail: kremena.makasheva@laplace.univ-tlse.fr; Laurent, C.
2014-09-22
Charge injection from a metal/insulator contact is a process promoting the formation of space charge in polymeric insulation largely used in thick layers in high voltage equipment. The internal charge perturbs the field distribution and can lead to catastrophic failure either through its electrostatic effects or through energetic processes initiated under charge recombination and/or hot electrons effects. Injection is still ill-described in polymeric insulation due to the complexity of the contact between the polymer chains and the electrodes. Barrier heights derived from the metal work function and the polymer electronic affinity do not provide a good description of the measurementsmore » [Taleb et al., IEEE Trans. Dielectr. Electr. Insul. 20, 311–320 (2013)]. Considering the difficulty to describe the contact properties and the need to prevent charge injection in polymers for high voltage applications, we developed an alternative approach by tailoring the interface properties by the silver nanoparticles (AgNPs)/plasma polymer stack, deposited on the polymer film. Due to their small size, the AgNPs, covered by a very thin film of plasma polymer, act as deep traps for the injected charges thereby stabilizing the interface from the point of view of charge injection. After a quick description of the method for elaborating the nanostructured layer near the contact, it is demonstrated how the AgNPs/plasma polymer stack effectively prevents, in a spectacular way, the formation of bulk space charge.« less
Wire Insulation Flammability Experiment: USML-1 One Year Post Mission Summary
NASA Technical Reports Server (NTRS)
Greenberg, Paul S.; Sacksteder, Kurt R.; Kashiwagi, Takashi
1994-01-01
Herein we report the results from the Wire Insulation Flammability (WIF) Experiment performed in the Glovebox Facility on the USML-1 mission. This experiment explored various aspects of electrically induced fire scenarios in a reduced gravity environment. Under quiescent microgravity conditions, heat and mass transfer are dominated by diffusive and radiative transport; while in normal-gravity buoyancy induced convection often dominates. Of considerable scientific and practical interest is the intermediate situation of combustion occurring in the presence of imposed gas flows, with lower characteristic velocities than those induced by buoyancy in noma1 gravity. Two distinct cases naturally arise: flow direction opposed to, or concurrent with, the flame spread direction. Two tests of each kind were conducted in the WIF experiment, providing the first controlled demonstration of flame spreading in forced convection ever conducted in space. Four test modules were flown. The wire insulation, 1.5 mm in diameter, was polyethylene, extruded onto nichrome wire. Temperatures of the wh3 cores and insulation heated in quiescent and flowing environments were measured. Video and still-camera images of the samples, burning in air flowing at approximately 10 cm/sec, were recorded to obtain flame characteristics including spread rate, structure and temperature. Flame spread rates in concurrent flow were approximately twice those in opposed flow. In concurrent and opposed flow regimes, the spreading flames stabilized around a bead of molten insulation material, within which bubble nucleation was observed. An ignition attempt without flow mated a quiescent cloud of vaporized fuel which ignited dramatically yet failed to sustain normal flame spread. Finally, all tests produced substantial soot agglomerates, particularly the concurrent flow tests; and the collected soot has a morphology very distinct from soot formed in normal gravity flames. Several unexpected and unique microgravity combustion phenomena were observed.
Self-supporting hydrogel stamps for the microcontact printing of proteins.
Coq, Naïs; van Bommel, Ties; Hikmet, Rifat A; Stapert, Hendrik R; Dittmer, Wendy U
2007-04-24
In this work we explore a new hydrogel stamp material obtained from polymerizing 2-hydroxyethyl acrylate and poly(ethylene glycol) diacrylate in the presence of water for the microcontact printing of proteins directly on gold substrates and by covalent coupling to self-assembled monolayers of alkanethiols. At high cross-link density, the hydrogel is rigid, hydrophilic, and with a high buffer holding capacity to enable the unsupported printing of protein patterns homogeneously and reproducibly, with micrometer-range precision. The stamps were used to print antibodies to human parathyroid hormone, which were shown using immunoassay tests to retain their biological function with binding capacities comparable to those of solution-adsorbed antibodies.
Study on Thermal Conductivities of Aromatic Polyimide Aerogels.
Feng, Junzong; Wang, Xin; Jiang, Yonggang; Du, Dongxuan; Feng, Jian
2016-05-25
Polyimide aerogels for low density thermal insulation materials were produced by 4,4'-diaminodiphenyl ether and 3,3',4,4'-biphenyltetracarboxylic dianhydride, cross-linked with 1,3,5-triaminophenoxybenzene. The densities of obtained polyimide aerogels are between 0.081 and 0.141 g cm(-3), and the specific surface areas are between 288 and 322 m(2) g(-1). The thermal conductivities were measured by a Hot Disk thermal constant analyzer. The value of the measured thermal conductivity under carbon dioxide atmosphere is lower than that under nitrogen atmosphere. Under pressure of 5 Pa at -130 °C, the thermal conductivity is the lowest, which is 8.42 mW (m K)(-1). The polyimide aerogels have lower conductivity [30.80 mW (m K)(-1)], compared to the value for other organic foams (polyurethane foam, phenolic foam, and polystyrene foam) with similar apparent densities under ambient pressure at 25 °C. The results indicate that polyimide aerogel is an ideal insulation material for aerospace and other applications.
Direct Fabrication of Inkjet-Printed Dielectric Film for Metal-Insulator-Metal Capacitors
NASA Astrophysics Data System (ADS)
Cho, Cheng-Lin; Kao, Hsuan-ling; Wu, Yung-Hsien; Chang, Li-Chun; Cheng, Chun-Hu
2018-01-01
In this study, an inkjet-printed dielectric film that used a polymer-based SU-8 ink was fabricated for use in a metal-insulator-metal (MIM) capacitor. Thermal treatment of the inkjet-printed SU-8 polymer film affected its surface morphology, chemical structure, and surface wettability. A 20-min soft-bake at 60°C was applied to eliminate inkjet-printed bubbles and ripples. The ultraviolet-exposed SU-8 polymer film was crosslinked at temperatures between 120°C and 220°C and became disordered at 270°C, demonstrated using Fourier-transform infrared spectroscopy. A maximum SU-8 polymer film hard-bake temperature of 120°C was identified, and a printing process was subsequently employed because the appropriate water contact angle of the printed film was 79°. Under the appropriate inkjet printing conditions, the two-transmission-line method was used to extract the dielectric and electrical properties of the SU-8 polymer film, and the electrical behavior of the fabricated MIM capacitor was also characterized.
Local Charge Injection and Extraction on Surface-Modified Al2O3 Nanoparticles in LDPE.
Borgani, Riccardo; Pallon, Love K H; Hedenqvist, Mikael S; Gedde, Ulf W; Haviland, David B
2016-09-14
We use a recently developed scanning probe technique to image with high spatial resolution the injection and extraction of charge around individual surface-modified aluminum oxide nanoparticles embedded in a low-density polyethylene (LDPE) matrix. We find that the experimental results are consistent with a simple band structure model where localized electronic states are available in the band gap (trap states) in the vicinity of the nanoparticles. This work offers experimental support to a previously proposed mechanism for enhanced insulating properties of nanocomposite LDPE and provides a powerful experimental tool to further investigate such properties.
Aging, Loss-of-Coolant Accident (LOCA), and high potential testing of damaged cables
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vigil, R.A.; Jacobus, M.J.
1994-04-01
Experiments were conducted to assess the effects of high potential testing of cables and to assess the survivability of aged and damaged cables under Loss-of-Coolant Accident (LOCA) conditions. High potential testing at 240 Vdc/mil on undamaged cables suggested that no damage was incurred on the selected virgin cables. During aging and LOCA testing, Okonite ethylene propylene rubber (EPR) cables with a bonded jacket experienced unexpected failures. The failures appear to be primarily related to the level of thermal aging and the presence of a bonded jacket that ages more rapidly than the insulation. For Brand Rex crosslinked polyolefin (XLPO) cables,more » the results suggest that 7 mils of insulation remaining should give the cables a high probability of surviving accident exposure following aging. The voltage necessary to detect when 7 mils of insulation remain on unaged Brand Rex cables is approximately 35 kVdc. This voltage level would almost certainly be unacceptable to a utility for use as a damage assessment tool. However, additional tests indicated that a 35 kvdc voltage application would not damage virgin Brand Rex cables when tested in water. Although two damaged Rockbestos silicone rubber cables also failed during the accident test, no correlation between failures and level of damage was apparent.« less
Stress-dependent voltage offsets from polymer insulators used in rock mechanics and material testing
NASA Astrophysics Data System (ADS)
Carlson, G. G.; Dahlgren, R.; Vanderbilt, V. C.; Johnston, M. J.; Dunson, C.; Gray, A.; Freund, F.
2013-12-01
Dielectric insulators are used in a variety of laboratory settings when performing experiments in rock mechanics, petrology, and electromagnetic studies of rocks in the fields of geophysics, material science, and civil engineering. These components may be used to electrically isolate geological samples from the experimental equipment, to perform a mechanical compliance function between brittle samples and the loading equipment, to match ultrasonic transducers, or perform other functions. In many experimental configurations the insulators bear the full brunt of force applied to the sample but do not need to withstand high voltages, therefore the insulators are often thin sheets of mechanically tough polymers. From an instrument perspective, transduction from various types of mechanical perturbation has been qualitatively compared for a number of polymers [1, 2] and these error sources are readily apparent during high-impedance measurements if not mitigated. However even when following best practices, a force-dependent voltage signal still remains and its behavior is explored in this presentation. In this experiment two thin sheets (0.25 mm) of high-density polyethylene (HDPE) were set up in a stack, held alternately between three aluminum bars; this stack was placed on the platen of a 60T capacity hydraulic testing machine. The surface area, A, over which the force is applied to the PE sheets in this sandwich is roughly 40 square cm, each sheet forming a parallel-plate capacitor having roughly 320 pF [3], assuming the relative dielectric permittivity of PE is ~2.3. The outer two aluminum bars were connected to the LO input of the electrometer and the central aluminum bar was connected to the HI input of a Keithley model 617 electrometer. Once the stack is mechanically well-seated with no air gaps, the voltage offset is observed to be a linear function of the baseline voltage for a given change in applied force. For a periodically applied force of 66.7 kN the voltage offsets were measured as a function of initial voltage, and these data were fit with a linear function that was constrained to pass through the origin. The best fit solution had a correlation coefficient of R = 0.85 and a slope of approximately -0.0228 volts/volt. The voltage offset when normalized is demonstrated to be constant -2.28 % for both positive and negative polarities over nearly 3 orders of baseline voltage magnitude. From this, the voltage-force coefficient is derived to be -0.34 ppm/N. This correlates well to a first-order parallel plate capacitor model that assumes constant area, and small deformation such that the polymer may be mechanically modeled by a spring that obeys Hooke's law. This simple model predicts that the coefficient of proportionality is a function of Young's modulus E = 0.8 GPa and surface area of the insulator, theoretically -1/EA = -0.31 ppm/N. The outcome of this work is an improved insulator made from ultra-high molecular weight (UHMW) polyethylene and other approaches toward the minimization of and compensation for these experimental artifacts. References: [1] Keithley Instruments, Low level measurements handbook, 'Choosing the best insulator,' 2-11 (2004). [2] Ibid., 2-26. [3] A. Skumiel, 'How to transform mechanical work into electrical energy using a capacitor,' European Journal of Physics 32, 625-630 (2011).
Three-Dimensional Nanometer Features of Direct Current Electrical Trees in Low-Density Polyethylene.
Pallon, Love K H; Nilsson, Fritjof; Yu, Shun; Liu, Dongming; Diaz, Ana; Holler, Mirko; Chen, Xiangrong R; Gubanski, Stanislaw; Hedenqvist, Mikael S; Olsson, Richard T; Gedde, Ulf W
2017-03-08
Electrical trees are one reason for the breakdown of insulating materials in electrical power systems. An understanding of the growth of electrical trees plays a crucial role in the development of reliable high voltage direct current (HVDC) power grid systems with transmission voltages up to 1 MV. A section that contained an electrical tree in low-density polyethylene (LDPE) has been visualized in three dimensions (3D) with a resolution of 92 nm by X-ray ptychographic tomography. The 3D imaging revealed prechannel-formations with a lower density with the width of a couple of hundred nanometers formed around the main branch of the electrical tree. The prechannel structures were partially connected with the main tree via paths through material with a lower density, proving that the tree had grown in a step-by-step manner via the prestep structures formed in front of the main channels. All the prechannel structures had a size well below the limit of the Paschen law and were thus not formed by partial discharges. Instead, it is suggested that the prechannel structures were formed by electro-mechanical stress and impact ionization, where the former was confirmed by simulations to be a potential explanation with electro-mechanical stress tensors being almost of the same order of magnitude as the short-term modulus of low-density polyethylene.
Hyaluronic acid based hydrogel system for soft tissue regeneration and drug delivery
NASA Astrophysics Data System (ADS)
Jha, Amit Kumar
We have developed hyaluronic acid (HA)-based, biomimetic hydrogel matrices that are hierarchically structured, mechanically robust and biologically active. Specifically, HA-based hydrogel particles (HGPs) with controlled sizes, defined porosity, and improved stability were synthesized using different inverse emulsion systems and crosslinking chemistries. The resultant particles either contained residual functional groups or were rendered reactive by subsequent chemical modifications. HA-based doubly crosslinked networks (DXNs) were synthesized via covalent crosslinking of HA HGPs with soluble HA macromers carrying mutually reactive functional groups. These hybrid matrices are hierarchical in nature, consisting of densely crosslinked HGPs integrated in a loosely connected secondary matrix. Their mechanical properties and degradation kinetics can be readily tuned by varying the particle size, functional group density, intra- and interparticle crosslinking. To improve the biological functions of HA HGPs, perlecan domain I (PlnDI), a basement membrane proteoglycan that has strong affinity for various heparin binding growth factors (HBGFs), was successfully conjugated to the particles through the core protein via a flexible poly(ethylene glycol) (PEG) linker. The immobilized PlnDI maintains its ability to bind bone morphogenetic proteins (BMP-2) and modulates its in vitro release. A similar, sustained release of BMP-2 was achieved by encapsulating BMP-2-loaded HGPs within a photocrosslinked HA matrix. When encapsulated in HA DXNs, primary bovine chondrocytes were able to maintain their phenotype, proliferate readily and produce abundant glycosaminoglycan. Finally, cell-adhesive HA DXNs were fabricated by encapsulating gelatin-decorated HA HGPs in a secondary HA matrix. Human MSCs were shown to adhere to the composite matrix through the focal adhesion sites clustered on particle surface. The cell-adhesive composite matrices supported hMSC proliferation and migration into the gels. Human MSCs were undifferentiated during the early time points of culture, however differentiated into osteoblast phenotype after 28 days of culture. In summary, the HA-based hydrogel matrices are hierarchically structured, mechanically robust and enzymatically stable, capable of mediating cellular functions through the spatial and temporal presentation of defined biological cues. These hydrogel systems are promising candidates for soft tissue regeneration.
Mechanically Strong Lightweight Materials for Aerospace Applications (x-aerogels)
NASA Technical Reports Server (NTRS)
Leventis, Nicholas
2005-01-01
The X-Aerogel is a new NASA-developed strong lightweight material made by reacting the mesoporous surfaces of 3-D networks of inorganic nanoparticles with polymeric crosslinkers. Since the relative amount of the crosslinker and the backbone are comparable, X-Aerogels can be viewed either as aerogels modified by templated accumulation of polymer on the skeletal nanoparticles, or as nanoporous polymers made by templated casting of polymeric precursors on a nanostructured framework. The most striking feature of X-Aerogels is that for a nominal 3-fold increase in density (still a ultralightweight material), the mechanical strength can be up to 300 times higher than the strength of the underlying native aerogel. Thus, X-Aerogels combine a multiple of the specific compressive strength of steel, with the thermal conductivity of styrofoam. XAerogels have been demonstrated with several polymers such as polyurethanes/polyureas, epoxies and polyolefins, while crosslinking of approximately 35 different oxide aerogels yields a wide variety of dimensionally stable, porous lightweight materials with interesting structural, magnetic and optical properties. X-Aerogels are evaluated for cryogenic rocket fuel storage tanks and for Advanced EVA suits, where they will play the dual role of the thermal insulator/structural material. Along the same lines, major impact is also expected by the use of X-Aerogels in structural components/thermal protection for small satellites, spacecrafts, planetary vehicles and habitats.
Dynamics of drinking water biofilm in flow/non-flow conditions.
Manuel, C M; Nunes, O C; Melo, L F
2007-02-01
Drinking water biofilm formation on polyvinyl chloride (PVC), cross-linked polyethylene (PEX), high density polyethylene (HDPE) and polypropylene (PP) was followed in three different reactors operating under stagnant or continuous flow regimes. After one week, a quasi-steady state was achieved where biofilm total cell numbers per unit surface area were not affected by fluctuations in the concentration of suspended cells. Metabolically active cells in biofilms were around 17-35% of the total cells and 6-18% were able to form colony units in R(2)A medium. Microbiological analysis showed that the adhesion material and reactor design did not affect significantly the biofilm growth. However, operating under continuous flow (0.8-1.9 Pa) or stagnant water had a significant effect on biofilm formation: in stagnant waters, biofilm grew to a less extent. By applying mass balances and an asymptotic biofilm formation model to data from biofilms grown on PVC and HDPE surfaces under turbulent flow, specific growth rates of bacteria in the biofilm were found to be similar for both materials (around 0.15 day(-1)) and much lower than the specific growth rates of suspended bacteria (around 1.8 day(-1)).
NASA Astrophysics Data System (ADS)
Wang, Guixia; Babaahmadi, Vahid; He, Nanfei; Liu, Yixin; Pan, Qin; Montazer, Majid; Gao, Wei
2017-11-01
All solid-state micro-supercapacitors (MSC) have emerged as attractive energy-storage units for portable and wearable electronics. Here, we describe a textile-based solid-state MSC via laser scribing of graphene oxide (GO) coatings on a flexible polyethylene terephthalate (PET) fabric. The laser-scribed graphene oxide layers (LGO) possess three-dimensionally porous structure suitable for electrochemical-double-layer formation. To improve the wash fastness and the flexibility of the as-prepared MSCs, glutaraldehyde (GA) was employed to crosslink the GO layers and PVA-gel electrolyte onto the PET fabric. The resultant all solid-state MSCs exhibited excellent flexibility, high areal specific capacitance (756 μF·cm-2 at 20 mV·s-1), and good rate capability when subject to bending and laundering. Furthermore, the MSC device showed a high power density of about 1.4 W·cm-3 and an energy density of 5.3 × 10-5 Wh·cm-3, and retained 98.3% of its initial capacitance after 1000 cycles at a current density of 0.5 mA·cm-2. This work is the first demonstration of in-plane MSCs on PET fabric surfaces with enhanced durability and flexibility.
Ahn, Jong Il; Kim, Gil Ah; Kwon, Hyo Suk; Ahn, Ji Yeon; Hubbell, Jeffrey A; Song, Yong Sang; Lee, Seung Tae; Lim, Jeong Mook
2015-01-01
This study was undertaken to examine how the softness of poly(ethylene) glycol (PEG)-based hydrogels, creating a three-dimensional (3D) microenvironment, influences the in vitro growth of mouse ovarian follicles. Early secondary, preantral follicles of 2 week-old mice were cultured in a crosslinked four-arm PEG hydrogel. The hydrogel swelling ratio, which relates to softness, was modified within the range 25.7–15.5 by increasing the reactive PEG concentration in the precursor solution from 5% to 15% w/v, but it did not influence follicular growth to form the pseudoantrum (60–80%; p = 0.76). Significant (p < 0.04) model effects, however, were detected in the maturation and developmental competence of the follicle-derived oocytes. A swelling ratio of > 21.4 yielded better oocyte maturation than other levels, while the highest competence to develop pronuclear and blastocyst formation was detected at 20.6. In conclusion, gel softness, as reflected in swelling ratio, was one of the essential factors for supporting folliculogenesis in vivo within a hydrogel-based, 3D microenvironment. © 2014 The Authors. Journal of Tissue Engineering and Regenerative Medicine published by John Wiley & Sons, Ltd. PMID:24493269
Saldarriaga Fernández, Isabel C; Busscher, Henk J; Metzger, Steve W; Grainger, David W; van der Mei, Henny C
2011-02-01
Biomaterial-associated infections (BAI) remain a serious clinical complication, often arising from an inability of host tissue-implant integration to out-compete bacterial adhesion and growth. A commercial polymer coating based on polyethylene glycol (PEG), available in both chemically inert and NHS-activated forms (OptiChem(®)), was compared for simultaneous growth of staphylococci and osteoblasts. In the absence of staphylococci, osteoblasts adhered and proliferated well on glass controls and on the NHS-reactive PEG-based coating over 48 h, but not on the inert PEG coating. Staphylococcal growth was low on both PEG-based coatings. When staphylococci were pre-adhered on surfaces for 1.5 h to mimic peri-operative contamination, osteoblast growth and spreading was reduced on glass but virtually absent on both reactive and inert PEG-based coatings. Thus although NHS-reactive, PEG-based coatings stimulated tissue-cell interactions in the absence of contaminating staphylococci, the presence of adhering staphylococci eliminated osteoblast adhesion advantages on the PEG surface. This study demonstrates the importance of using bacterial and cellular co-cultures compared to monocultures when assessing functionalized biomaterials coatings for infectious potential. Copyright © 2010 Elsevier Ltd. All rights reserved.
Deng, Shawn; Hassan, Mohammad K.; Nalawade, Amol; ...
2015-09-16
Hot (at 120 °C) and dry (20% relative humidity) operating conditions benefit fuel cell designs based on proton exchange membranes (PEMs) and hydrogen due to simplified system design and increasing tolerance to fuel impurities. In this paper, presented are preparation, partial characterization, and multi-scale modeling of such PEMs based on cross-linked, sulfonated poly(1,3-cyclohexadiene) (xsPCHD) blends and block copolymers with poly(ethylene glycol) (PEG). These low cost materials have proton conductivities 18 times that of current industry standard Nafion at hot, dry operating conditions. Among the membranes studied, the blend xsPCHD-PEG PEM displayed the highest proton conductivity, which exhibits a morphology withmore » higher connectivity of the hydrophilic domain throughout the membrane. Simulation and modeling provide a molecular level understanding of distribution of PEG within this hydrophilic domain and its relation to proton conductivities. Finally, this study demonstrates enhancement of proton conductivity at high temperature and low relative humidity by incorporation of PEG and optimized sulfonation conditions.« less
Selective laser sintering of ultra high molecular weight polyethylene for clinical applications.
Rimell, J T; Marquis, P M
2000-01-01
Rapid prototyping is a relatively new technology, which although prominent in the engineering industry is only just starting to make an impact in the medical field. Its current medical uses are mainly confined to surgical planning and teaching, but the technology also has the potential to allow for patient-tailored prostheses. The work reported here describes the application of a simplified selective laser sintering apparatus with ultra high molecular weight polyethylene (UHMWPE). The morphology and chemistry of the starting powders and lased material have been characterized using Fourier Transform Infra Red spectroscopy and a combination of light and scanning electron microscopy. It was found that solid linear continuous bodies could be formed, but material shrinkage caused problems when trying to form sheet-like structures. The porosity of the formed material was also a concern. The material exposed to the laser beam was shown to have undergone degradation in terms of chain scission, cross-linking, and oxidation. It has been concluded that to apply this technology to the fabrication of UHMWPE devices requires the development of improved starting powders, in particular with increased density. Copyright 2000 John Wiley & Sons, Inc.
Next Generation Hemostatic Materials Based on NHS-Ester Functionalized Poly(2-oxazoline)s.
Boerman, Marcel A; Roozen, Edwin; Sánchez-Fernández, María José; Keereweer, Abraham R; Félix Lanao, Rosa P; Bender, Johan C M E; Hoogenboom, Richard; Leeuwenburgh, Sander C; Jansen, John A; Van Goor, Harry; Van Hest, Jan C M
2017-08-14
In order to prevent hemorrhage during surgical procedures, a wide range of hemostatic agents have been developed. However, their efficacy is variable; hemostatic devices that use bioactive components to accelerate coagulation are dependent on natural sources, which limits reproducibility. Hybrid devices in which chain-end reactive poly(ethylene glycol) is employed as active component sometimes suffer from irregular cross-linking and dissolution of the polar PEG when blood flow is substantial. Herein, we describe a synthetic, nonbioactive hemostatic product by coating N-hydroxysuccinimide ester (NHS)-functional poly(2-oxazoline)s (POx-NHS) onto gelatin patches, which acts by formation of covalent cross-links between polymer, host blood proteins, gelatin and tissue to seal the wound site and prevent hemorrhage during surgery. We studied different process parameters (including polymer, carrier, and coating technique) in direct comparison with clinical products (Hemopatch and Tachosil) to obtain deeper understanding of this class of hemostatic products. In this work, we successfully prove the hemostatic efficacy of POx-NHS as polymer powders and coated patches both in vitro and in vivo against Hemopatch and Tachosil, demonstrating that POx-NHS are excellent candidate polymers for the development of next generation hemostatic patches.
Kim, Jong Oh; Oberoi, Hardeep S.; Desale, Swapnil; Kabanov, Alexander V.; Bronich, Tatiana K.
2014-01-01
Polymer nanogels have gained considerable attention as a potential platform for drug delivery applications. Here we describe the design and synthesis of novel polypeptide-based nanogels with hydrophobic moieties in the cross-linked ionic cores. Diblock copolymer, poly(ethylene glycol)-b-poly(L-glutamic acid), hydrophobically modified with L-phenylalanine methyl ester moieties was used for controlled template synthesis of nanogels with small size (ca. 70 nm in diameter) and narrow particle size distribution. Steady-state and time-resolved fluorescence studies using coumarin C153 indicated the existence of hydrophobic domains in the ionic cores of the nanogels. Stable doxorubicin-loaded nanogels were prepared at high drug capacity (30 w/w%). We show that nanogels are enzymatically-degradable leading to accelerated drug release under simulated lysosomal acidic pH. Furthermore, we demonstrate that the nanogel-based formulation of doxorubicin is well tolerated and exhibit an improved antitumor activity compared to a free doxorubicin in an ovarian tumor xenograft mouse model. Our results signify the point to a potential of these biodegradable nanogels as attractive carriers for delivery of chemotherapeutics. PMID:23998716
Madkou, Sherif; Melnichu, Iurii; Choukourov, Andrei; Krakovsky, Ivan; Biederman, Hynek; Schönhals, Andreas
2016-04-28
In recent years, highly cross-linked plasma polymers have started to unveil their potential in numerous biomedical applications in thin-film form. However, conventional diagnostic methods often fail due to their diverse molecular dynamics conformations. Here, glassy dynamics and the melting transition of thin PEO-like plasma assisted deposited (ppPEO) films (thickness 100 nm) were in situ studied by a combination of specific heat spectroscopy, utilizing a pJ/K sensitive ac-calorimeter chip, and composition analytical techniques. Different cross-linking densities were obtained by different plasma powers during the deposition of the films. Glassy dynamics were observed for all values of the plasma power. It was found that the glassy dynamics slows down with increasing the plasma power. Moreover, the underlying relaxation time spectra broaden indicating that the molecular motions become more heterogeneous with increasing plasma power. In a second set of the experiment, the melting behavior of the ppPEO films was studied. The melting temperature of ppPEO was found to decrease with increasing plasma power. This was explained by a decrease of the order in the crystals due to formation of chemical defects during the plasma process.
NASA Astrophysics Data System (ADS)
Reinholds, I.; Kalkis, V.; Zicans, J.; Merijs Meri, R.; Bockovs, I.; Grigalovica, A.; Muizzemnieks, G.
2013-12-01
Poly(ethylene-1-octene) copolymer (POE) composites filled with nickel-zinc ferrite nanoparticles have been modified by exposure to an electron beam at doses up to 500 kGy. The influence of radiation dose and ferrite content on mechanical properties has been investigated. Thermomechanical properties - thermorelaxation stresses formed in thermal heating and thermo residual stresses resulting in the process of full setting and cooling of materials have been investigated for radiation cross-linked oriented (extended up to 100%) composite samples. Increase of concentration of ferrite particles and increase of radiation dose affects a notable increase of elastic modulus and reduces the deformability in comparison to entire elastomer. Improvement of thermomechanical properties especially at low irradiation doses (100-150 kGy) have been detected for composites with increase of ferrite filler content up to 5 wt. %. It was found that gel content of POE increased up to 85% for pristine POE material with increase of irradiation dose up to 500 kGy due to the formation of cross-linked structure, increase of filler concentration up to 5 wt. % affect reduction in gel fraction due to uniform dispersion in amorphous (ethylene and substituted with hexyl branches) POE phases.
Ismaya, Wangsa Tirta; Hasan, Khomaini; Kardi, Idar; Zainuri, Amalia; Rahmawaty, Rinrin Irma; Permanahadi, Satyawisnu; El Viera, Baiq Vera; Harinanto, Gunawan; Gaffar, Shabarni; Natalia, Dessy; Subroto, Toto; Soemitro, Soetijoso
2013-05-01
α-Amylase catalyzes hydrolysis of starch to oligosaccharides, which are further degraded to simple sugars. The enzyme has been widely used in food and textile industries and recently, in generation of renewable energy. An α-amylase from yeast Saccharomycopsis fibuligera R64 (Sfamy) is active at 50 °C and capable of degrading raw starch, making it attractive for the aforementioned applications. To improve its characteristics as well as to provide information for structural study ab initio, the enzyme was chemically modified by acid anhydrides (nonpolar groups), glyoxylic acid (GA) (polar group), dimethyl adipimidate (DMA) (cross-linking), and polyethylene glycol (PEG) (hydrophilization). Introduction of nonpolar groups increased enzyme stability up to 18 times, while modification by a cross-linking agent resulted in protection of the calcium ion, which is essential for enzyme activity and integrity. The hydrophilization with PEG resulted in protection against tryptic digestion. The chemical modification of Sfamy by various modifiers has thereby resulted in improvement of its characteristics and provided systematic information beneficial for structural study of the enzyme. An in silico structural study of the enzyme improved the interpretation of the results.
Super stretchable electroactive elastomer formation driven by aniline trimer self-assembly
Chen, Jing; Guo, Baolin; Eyster, Thomas W.; Ma, Peter X.
2015-01-01
Biomedical electroactive elastomers with a modulus similar to that of soft tissues are highly desirable for muscle, nerve, and other soft tissue replacement or regeneration, but have rarely been reported. In this work, superiorly stretchable electroactive polyurethane-urea elastomers were designed based on poly(lactide), poly(ethylene glycol), and aniline trimer (AT). A strain at break higher than 1600% and a modulus close to soft tissues was achieved from these copolymers. The mechanisms of super stretchability of the copolymer were systematically investigated. Crystallinity, chemical cross-linking, ionic cross-linking and hard domain formation were examined using differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS), nuclear magnetic resonance (NMR) measurements and transmission electron microscopy (TEM). The sphere-like hard domains self-assembled from AT segments were found to provide the crucial physical interactions needed for the novel super elastic material formation. These super stretchable copolymers were blended with conductive fillers such as polyaniline nanofibers and nanosized carbon black to achieve a high electric conductivity of 0.1 S/cm while maintaining an excellent stretchability and a modulus similar to that of soft tissues (lower than 10 MPa). PMID:26692638
Sköldenberg, Olof; Rysinska, Agata; Chammout, Ghazi; Salemyr, Mats; Muren, Olle; Bodén, Henrik; Eisler, Thomas
2016-07-07
In vitro, Vitamin-E-diffused, highly cross-linked polyethylene (PE) has been shown to have superior wear resistance and improved mechanical properties when compared to those of standard highly cross-linked PE liners used in total hip arthroplasty (THA). The aim of the study is to evaluate the safety of a new cemented acetabular cup with Vitamin-E-doped PE regarding migration, head penetration and clinical results. In this single-centre, double-blinded, randomised controlled trial, we will include 50 patients with primary hip osteoarthritis scheduled for THA and randomise them in a 1:1 ratio to a cemented cup with either argon gas-sterilised PE (control group) or Vitamin-E-diffused PE (vitamin-e group). All patients and the assessor of the primary outcome will be blinded and the same uncemented stem will be used for all participants. The primary end point will be proximal migration of the cup at 2 years after surgery measured with radiostereometry. Secondary end points include proximal migration at other follow-ups, total migration, femoral head penetration, clinical outcome scores and hip-related complications. Patients will be followed up at 3 months and at 1, 2, 5 and 10 years postoperatively. Results will be analysed using 95% CIs for the effect size. A regression model will also be used to adjust for stratification factors. The ethical committee at Karolinska Institutet has approved the study. The first results from the study will be disseminated to the medical community via presentations and publications in relevant medical journals when the last patient included has been followed up for 2 years. NCT02254980. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/
A Novel Method to Assess Wear Rates of Retrieved Tibial Inserts Following in-vivo Use
NASA Astrophysics Data System (ADS)
Paniogue, Tanille J.
Ultra-high molecular weight polyethylene (UHMWPE) on cobalt chrome is the bearing couple of choice for total knee arthroplasty. The number of patients undergoing total knee arthroplasty has been steadily growing and is projected to continue increasing rapidly in the near future. Many of these patients are younger and more active and therefore need a longer lasting device. However, many of these devices fail prematurely and often the primary reason for failure and ultimately revision is due to wear related issues. Therefore, examining how wear rates of the UHMWPE tibial insert change during in-vivo use can help elucidate the mechanisms of accelerated wear and hopefully aid in finding solutions to combat wear related failures. Different crosslinking treatments have been employed by manufacturers to improve wear resistance of the polyethylene. While this has been shown to be an effective way to reduce wear, crosslinking has led to other issues such as oxidative instability and a decline in mechanical properties. The purpose of this body of work is to examine how changes in oxidation, after in-vivo use, affect wear resistance. A novel testing method was developed to test the native articular surface from retrieved tibial inserts in a laboratory Pin-on-Disk (POD) simulator. The method was validated using short-duration implant articular surfaces and non-articular control pins. In the absence of high surface oxidation or severe surface damage, the articular surface pins had comparable steady state wear rates to their bulk counterparts. Tests of devices with longer in-vivo service show chemical changes consistent with a free-radical mediated oxidation mechanism. Tribological assessment of the articular surfaces shows increasing wear rates as a function of oxidation. While this relationship has been hypothesized in the literature, these experiments represent the first physical demonstration of the phenomenon. The wear mechanism is further explored through infrared spectroscopy, assessment of the wear scar, and documentation of evolution of the contact surfaces in the articulation.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Krause, B., E-mail: krause-beate@ipfdd.de, E-mail: poe@ipfdd.de, E-mail: gohs@ipfdd.de; Pötschke, P., E-mail: krause-beate@ipfdd.de, E-mail: poe@ipfdd.de, E-mail: gohs@ipfdd.de; Gohs, U., E-mail: krause-beate@ipfdd.de, E-mail: poe@ipfdd.de, E-mail: gohs@ipfdd.de
2014-05-15
Polymer modification with high energy electrons (EB) is well established in different applications for many years. It is used for crosslinking, curing, degrading, grafting of polymeric materials and polymerisation of monomers. In contrast to this traditional method, electron induced reactive processing (EIReP) combines the polymer modification with high energy electrons and the melt mixing process. This novel reactive method was used to prepare polymer blends and composites. In this study, both methods were used for the preparation of polyethylene (PE)/ multiwalled carbon nanotubes (MWCNT) composites in the presence of a coupling agent. The influence of MWCNT and type of electronmore » treatment on the gel content, the thermal conductivity, rheological, and electrical properties was investigated whereby as-grown and oxidised MWCNT were used. In the presence of a coupling agent and at an absorbed dose of 40 kGy, the gel content increased from 57 % for the pure PE to 74 % or 88 % by the addition of as-grown (Baytubes® C150P) or oxidised MWCNT, respectively. In comparison to the composites containing the as-grown MWCNTs, the use of the oxidised MWCNTs led to higher melt viscosity and higher storage modulus due to higher yield of filler polymer couplings. The melt viscosity increased due to the addition of MWCNT and crosslinking of PE. The thermal conductivity increased to about 150 % and showed no dependence on the kind of MWCNT and the type of electron treatment. In contrast, the lowest value of electrical volume resistivity was found for the non-irradiated samples and after state of the art electron treatment without any influence of the type of MWCNT. In the case of EIReP, the volume resistivity increased by 2 (as-grown MWCNT) or 3 decades (oxidised MWCNT) depending on the process parameters.« less
NASA Astrophysics Data System (ADS)
Halstenberg, Sven
2002-01-01
The goal of the research presented in this dissertation was to create a biomimetic artificial material that exhibits functions of extracellular matrix relevant for improved nerve regeneration. Neural adhesion peptides were photoimmobilized on highly crosslinked poly(ethylene glycol)-based substrates that were otherwise non-adhesive. Neurons adhered in two-dimensional patterns for eleven hours, but no neurites extended. To enable neurite extension and nerve regeneration in three dimensions, and to address the need for specifically cell adhesive and cell degradable materials for clinical applications in tissue repair in general, an artificial protein was recombinantly expressed and purified that consisted of a repeating amino acid sequence based on fibrinogen and anti-thrombin III. The recombinant protein contained integrin-binding RGD sites, plasmin degradation sites, heparin binding sites, and six thiol-containing cysteine residues as grafting sites for poly(ethylene glycol) diacrylate via Michael-type conjugate addition. The resulting protein-graft-poly(ethylene glycol)acrylates were crosslinked by photopolymerization to form hydrogels. Although three-dimensional, RGD mediated and serine protease-dependent ingrowth of human fibroblasts into protein-graft-poly(ethylene glycol) hydrogels occurred, only surface neurite outgrowth was observed from chick dorsal root ganglia. Axonal outgrowth depended on the concentration of matrix-bound heparin, suggesting that improved mechanical strength of the hydrogels and possible immobilization of neuroactive factors due to the presence of heparin promoted neurite outgrowth. Together, the above results show that specific biological functions can be harnessed by protein-graft-poly(ethylene glycol) hydrogels to serve as matrices for tissue repair and regeneration. In particular, the two design objectives, specific cell adhesion and degradability by cell-associated proteases, were fulfilled by the material. In the future, this and similar artificial protein-graft-poly(ethylene glycol) materials with varying protein elements for improved wound healing might serve as biosynthetic implant materials or wound dressings that degrade in synchrony with the formation of a variety of target tissues.
Sköldenberg, Olof; Rysinska, Agata; Chammout, Ghazi; Salemyr, Mats; Muren, Olle; Bodén, Henrik; Eisler, Thomas
2016-01-01
Introduction In vitro, Vitamin-E-diffused, highly cross-linked polyethylene (PE) has been shown to have superior wear resistance and improved mechanical properties when compared to those of standard highly cross-linked PE liners used in total hip arthroplasty (THA). The aim of the study is to evaluate the safety of a new cemented acetabular cup with Vitamin-E-doped PE regarding migration, head penetration and clinical results. Methods and analysis In this single-centre, double-blinded, randomised controlled trial, we will include 50 patients with primary hip osteoarthritis scheduled for THA and randomise them in a 1:1 ratio to a cemented cup with either argon gas-sterilised PE (control group) or Vitamin-E-diffused PE (vitamin-e group). All patients and the assessor of the primary outcome will be blinded and the same uncemented stem will be used for all participants. The primary end point will be proximal migration of the cup at 2 years after surgery measured with radiostereometry. Secondary end points include proximal migration at other follow-ups, total migration, femoral head penetration, clinical outcome scores and hip-related complications. Patients will be followed up at 3 months and at 1, 2, 5 and 10 years postoperatively. Results Results will be analysed using 95% CIs for the effect size. A regression model will also be used to adjust for stratification factors. Ethics and dissemination The ethical committee at Karolinska Institutet has approved the study. The first results from the study will be disseminated to the medical community via presentations and publications in relevant medical journals when the last patient included has been followed up for 2 years. Trial registration number NCT02254980. PMID:27388352
Cole, Adam J.; David, Allan E.; Wang, Jianxin; Galbán, Craig J.; Hill, Hannah L.; Yang, Victor C.
2010-01-01
While successful magnetic tumor targeting of iron oxide nanoparticles has been achieved in a number of models, the rapid blood clearance of magnetically suitable particles by the reticuloendothelial system (RES) limits their availability for targeting. This work aimed to develop a long-circulating magnetic iron oxide nanoparticle (MNP) platform capable of sustained tumor exposure via the circulation and, thus, enhanced magnetic tumor targeting. Aminated, cross-linked starch (DN) and aminosilane (A) coated MNPs were successfully modified with 5 kDa (A5, D5) or 20 kDa (A20, D20) polyethylene glycol (PEG) chains using simple N-Hydroxysuccinimide (NHS) chemistry and characterized. Identical PEG-weight analogues between platforms (A5 & D5, A20 & D20) were similar in size (140–190 nm) and relative PEG labeling (1.5% of surface amines – A5/D5, 0.4% – A20/D20), with all PEG-MNPs possessing magnetization properties suitable for magnetic targeting. Candidate PEG-MNPs were studied in RES simulations in vitro to predict long-circulating character. D5 and D20 performed best showing sustained size stability in cell culture medium at 37°C and 7 (D20) to 10 (D5) fold less uptake in RAW264.7 macrophages when compared to previously targeted, unmodified starch MNPs (D). Observations in vitro were validated in vivo, with D5 (7.29 hr) and D20 (11.75 hr) showing much longer half-lives than D (0.12 hr). Improved plasma stability enhanced tumor MNP exposure 100 (D5) to 150 (D20) fold as measured by plasma AUC0-∞ Sustained tumor exposure over 24 hours was visually confirmed in a 9L-glioma rat model (12 mg Fe/kg) using magnetic resonance imaging (MRI). Findings indicate that both D5 and D20 are promising MNP platforms for enhanced magnetic tumor targeting, warranting further study in tumor models. PMID:21176955
Polyimide Aerogels with Three-Dimensional Cross-Linked Structure
NASA Technical Reports Server (NTRS)
Panek, John
2010-01-01
Polyimide aerogels with three-dimensional cross-linked structure are made using linear oligomeric segments of polyimide, and linked with one of the following into a 3D structure: trifunctional aliphatic or aromatic amines, latent reactive end caps such as nadic anhydride or phenylethynylphenyl amine, and silica or silsesquioxane cage structures decorated with amine. Drying the gels supercritically maintains the solid structure of the gel, creating a polyimide aerogel with improved mechanical properties over linear polyimide aerogels. Lightweight, low-density structures are desired for acoustic and thermal insulation for aerospace structures, habitats, astronaut equipment, and aeronautic applications. Aerogels are a unique material for providing such properties because of their extremely low density and small pore sizes. However, plain silica aerogels are brittle. Reinforcing the aerogel structure with a polymer (X-Aerogel) provides vast improvements in strength while maintaining low density and pore structure. However, degradation of polymers used in cross-linking tends to limit use temperatures to below 150 C. Organic aerogels made from linear polyimide have been demonstrated, but gels shrink substantially during supercritical fluid extraction and may have lower use temperature due to lower glass transition temperatures. The purpose of this innovation is to raise the glass transition temperature of all organic polyimide aerogel by use of tri-, tetra-, or poly-functional units in the structure to create a 3D covalently bonded network. Such cross-linked polyimides typically have higher glass transition temperatures in excess of 300 400 C. In addition, the reinforcement provided by a 3D network should improve mechanical stability, and prevent shrinkage on supercritical fluid extraction. The use of tri-functional aromatic or aliphatic amine groups in the polyimide backbone will provide such a 3D structure.
NASA Astrophysics Data System (ADS)
Van Lancker, Marc; Herer, Arnold; Cleland, Marshall R.; Jongen, Yves; Abs, Michel
1999-05-01
The Rhodotron is a high-voltage, high-power electron beam accelerator based on a design concept first proposed in 1989 by J. Pottier of the French Atomic Agency, Commissariat à l'Energie Atomique (CEA). In December 1991, the Belgian particle accelerator manufacturer, Ion Beam Applications s.a. (IBA) entered into an exclusive agreement with the CEA to develop and industrialize the Rhodotron. Electron beams have long been used as the preferential method to cross-link a variety of polymers, either in their bulk state or in their final form. Used extensively in the wire and cable industry to toughen insulating jackets, electron beam-treated plastics can demonstrate improved tensile and impact strength, greater abrasion resistance, increased temperature resistance and dramatically improved fire retardation. Electron beams are used to selectively cross-link or degrade a wide range of polymers in resin pellets form. Electron beams are also used for rapid curing of advanced composites, for cross-linking of floor-heating and sanitary pipes and for cross-linking of formed plastic parts. Other applications include: in-house and contract medical device sterilization, food irradiation in both electron and X-ray modes, pulp processing, electron beam doping of semi-conductors, gemstone coloration and general irradiation research. IBA currently markets three models of the Rhodotron, all capable of 10 MeV and alternate beam energies from 3 MeV upwards. The Rhodotron models TT100, TT200 and TT300 are typically specified with guaranteed beam powers of 35, 80 and 150 kW, respectively. Founded in 1986, IBA, a spin-off of the Cyclotron Research Center at the University of Louvain (UCL) in Belgium, is a pioneer in accelerator design for industrial-scale production.
Hussey, Daniel K; McGrory, Brian J
2017-08-01
Mechanically assisted crevice corrosion (MACC) in metal-on-polyethylene total hip arthroplasty (THA) is of concern, but its prevalence, etiology, and natural history are incompletely understood. From January 2003 to December 2012, 1352 consecutive THA surgeries using a titanium stem, cobalt-chromium alloy femoral head, and highly cross-linked polyethylene liner from a single manufacturer were performed. Patients were followed at 1-year and 5-year intervals for surveillance, but also seen earlier if they had symptoms. Any patient with osteolysis >1 cm (n = 3) or unexplained pain (n = 85) underwent examination, radiographs, complete blood count, erythrocyte sedimentation rate, and C-reactive protein, as well as tests for serum cobalt and chromium levels. Symptomatic MACC was present in 43 of 1352 patients (3.2%). Prevalence of MACC by year of implant ranged from 0% (0 of 61, 2003; 0 of 138, 2005) to 10.5% (17 of 162; 2009). The M/L Taper stem had a greater prevalence (4.9%) of MACC than all other Zimmer (Zimmer, Inc, Warsaw, IN) 12/14 trunnion stem types combined (1.2%; P < .001). Twenty-seven of 43 (62.8%) patients have undergone revision surgery, and 16 of 43 (37.2%) patients have opted for ongoing surveillance. Comparing symptomatic THA patients with and without MACC, no demographic, clinical, or radiographic differences were found. MACC was significantly more common in 0 length femoral heads (compared with both -3.5 mm and +3.5 mm heads). The prevalence of MACC in metal-on-polyethylene hips is higher in this cross-sectional study than previously reported. A significantly higher prevalence was found in patients with M/L Taper style stem and THA performed both in 2009 and also between 2009 and 2012 with this manufacturer. Copyright © 2017 Elsevier Inc. All rights reserved.
Antibody loaded collapsible hyaluronic acid hydrogels for intraocular delivery.
Egbu, Raphael; Brocchini, Steve; Khaw, Peng T; Awwad, Sahar
2018-03-01
Injectable gels have the potential to encapsulate drugs for sustained release of protein therapeutics for use in the eye. Hyaluronic acid (HA) is a biodegradable clinically used material and poly N-isopropylacrylamide (pNIPAAM) is a stimuli responsive polymer that can display a lower critical solution temperature (LCST) at physiological conditions. Two gel systems incorporating HA were prepared in the presence of the antibody infliximab (INF): i) 1% and 5% tyramine-substituted HA (HA-Tyr) was enzymatically crosslinked in the presence of INF to form HA-Tyr-INF and ii) NIPAAM was chemically crosslinked in the presence of HA and INF with 1 and 3% poly(ethylene glycol) diacrylate (PEGDA) to form PEGDA-pNIPAAM-HA-INF. The PEGDA-pNIPAAM-HA-INF hydrogels displayed LCSTs at temperatures ranging from 31.4 ± 0.2 to 35.7 ± 0.3 °C. Although all the gels prepared were injectable, INF-loaded gels with lower crosslinking density (1% PEGDA-pNIPAAM-HA and 1% HA-Tyr) showed lower elastic (G') and viscous (G″) moduli compared to higher crosslinked gels (3% PEGDA-pNIPAAM-HA-INF and 5% HA-Tyr-INF) resulting in differences in swelling ratio (SR). Moduli may be correlated with overall stiffness of the gel. All hydrogels demonstrated sustained release of INF in a two-compartment in vitro outflow model of the human eye called the PK-Eye. The 1% PEGDA-pNIPAAM-HA-INF hydrogel displayed the slowest release (24.9 ± 0.4% INF release by day 9) in phosphate buffered saline (PBS, pH 7.4), which is a better release profile than the free drug alone (tested under the same conditions). These results suggest that PEGDA-pNIPAAM-HA has potential for the continued development of formulations to prolong the intraocular release of proteins. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Nakatsuka, Matthew Allan Masao
Microbubbles, consisting of gas-filled cores encapsulated within phospholipid or polymer shells, are the most widely used ultrasound contrast agents in the world. Because of their acoustic impedance mismatch with surrounding tissues and compressible gaseous interiors, they have high echogenicities that allow for efficient backscatter of ultrasound. They can also generate unique harmonic frequencies when insonated near their resonance frequency, depending on physical microbubble properties such as the stiffness and thickness of the encapsulating shell. Microbubbles are used to detect a number of cardiovascular diseases, but current methodologies lack the ability to detect and distinguish small, rapidly growing abnormalities that do not produce visible blockage or slowing of blood flow. This work describes the development, formulation, and validation of microbubbles with various polymer shell architectures designed to modulate their acoustic ability. We demonstrate that the addition of a thick disulfide crosslinked, poly(acrylic acid) encapsulating shell increases a bubble's resistance to cavitation and changes its resonance frequency. Modification of this shell architecture to use hybridized DNA strands to form crosslinks between the polymer chains allows for tuning of the bubble acoustic response. When the DNA crosslinks are in place, shell stiffness is increased so the bubbles do not oscillate and acoustic signal is muted. Subsequently, when these DNA strands are displaced, partial acoustic activity is restored. By using aptamer sequences with a specific affinity towards the biomolecule thrombin as the DNA crosslinking strand, this acoustic "ON/OFF" behavior can be specifically tailored towards the presence of a specific biomarker, and produces a change in acoustic signal at concentrations of thrombin consistent with acute deep venous thrombosis. Incorporation of the emulsifying agent poly(ethylene glycol) into the encapsulating shell improves microbubble yield and circulation half-life substantially, allowing for the in vivo detection of a blood clot in a rabbit model. The results presented here show a unique marriage of highly specific molecular imaging and sonography that could be tailored towards a wide variety of cardiovascular abnormalities.
NASA Astrophysics Data System (ADS)
Schwartz, Christian John
The performance of several synthetic biomaterials and bovine articular cartilage were investigated in terms of their suitability for use as articulating surfaces in artificial joints. The Dual-Axis Wear Simulator (DAWS), a wear testing machine that simulates conditions in a synovial joint, was designed and fabricated to enable investigators to measure the wear of such materials in multi-directional sliding while immersed in a bovine serum lubricant solution. This machine was used initially to determine the wear mechanisms and wear amounts of ultra-high molecular weight polyethylene (UHMWPE), polytetrafluoroethylene (PTFE), polyoxymethylene (POM), and the compliant elastomer Pellethane(TM) 2363-80A. It was found that the compliant material produced lower wear. Dynamic mechanical analysis was used to determine that bovine articular cartilage had a very significant amount of viscoelasticity to support static loads and damp impact loads. Furthermore, the use of a compliant counterface led to lower wear in the cartilage as compared to a rigid counterface. Pt-Zr quasicrystals were used as fillers in UHMWPE, and the wear, stiffness, and impact toughness of the filled polymer were shown to be comparable or better than those of UHMWPE that had been irradiation crosslinked. Crosslinked UHMWPE was investigated for its susceptibility to oxidative degradation and increased wear. It was found that thermal stabilization of the polymer could be eliminated if a mild amount crosslinking was used. Furthermore, there was no degradation in wear resistance of mildly crosslinked and non-stabilized UHMWPE even after accelerated aging. Based on the results of this work and lessons learned about compliance and wear resistance, blends were produced by using surface-activated UHMWPE particles as fillers in elastomeric PUR. The blends showed better wear resistance than UHMWPE, as well as increased stiffness and damping over PUR. The results of this work indicated that there is great potential for the development of new biomaterials and materials treatment methods to produce more durable articulating components in artificial joints.
Wang, Yuqiang; Su, Jing; Cai, Wenwei; Lu, Ping; Yuan, Lifen; Jin, Tuo; Chen, Shuyan; Sheng, Jing
2013-01-01
Biscarbamate cross-linked polyethylenimine derivative (PEI-Et) has been reported as a novel nonviral vector for efficient and safe gene transfer in our previous work. However, it had no cell-specificity. To achieve specific delivery of genes to hepatocytes, galactosylated poly(ethylene glycol)-graft-polyethylenimine derivative (GPE) was prepared through modification of PEI-Et with poly(ethylene glycol) and lactobionic acid, bearing a galactose group as a hepatocyte-targeting moiety. The composition of GPE was characterized by proton nuclear magnetic resonance. The weight-average molecular weight of GPE measured with a gel permeation chromatography instrument was 9489 Da, with a polydispersity of 1.44. GPE could effectively condense plasmid DNA (pDNA) into nanoparticles. Gel retardation assay showed that GPE/pDNA complexes were completely formed at weigh ratios (w/w) over 3. The particle size of GPE/pDNA complexes was 79–100 nm and zeta potential was 6–15 mV, values which were appropriate for cellular uptake. The morphology of GPE/pDNA complexes under atomic force microscopy appeared spherical and uniform in size, with diameters of 53–65 nm. GPE displayed much higher transfection efficiency than commercially available PEI 25 kDa in BRL-3A cell lines. Importantly, GPE showed good hepatocyte specificity. Also, the polymer exhibited significantly lower cytotoxicity compared to PEI 25 kDa at the same concentration or weight ratio in BRL-3A cell lines. To sum up, our results indicated that GPE might carry great potential in safe and efficient hepatocyte-targeting gene delivery. PMID:23576866
NASA Astrophysics Data System (ADS)
Ayoob, Raed; Alhabill, Fuad N.; Andritsch, Thomas; Vaughan, Alun S.
2018-02-01
The effect of water absorption on the dielectric response of polyethylene/hexagonal boron nitride nanocomposites has been studied by dielectric spectroscopy. The nanocomposites have been prepared with hBN concentrations ranging from 2 wt% to 30 wt%. Fourier transform infrared spectroscopy and thermogravimetric analysis revealed a very small amount of hydroxyl groups on the surface of hBN. Mass loss measurements showed that the nanocomposites did not absorb any water under ambient and dry conditions while there was some water absorption under wet conditions. The dielectric spectroscopy results showed a broad relaxation peak, indicative of different states of water with water shells of different thickness, which moved to higher frequencies with increasing water content. However, the dielectric losses were significantly lower than the losses reported in the literature of nanocomposites under wet conditions. In addition, all the absorbed water was successfully removed under vacuum conditions which demonstrated that the interactions between the water and the nanocomposites were very weak, due to the hydrophobic nature of the hBN surface. This is a highly useful property, when considering these materials for applications in electrical insulation.
Thermal gelation and tissue adhesion of biomimetic hydrogels
Burke, Sean A; Ritter-Jones, Marsha; Lee, Bruce P; Messersmith, Phillip B
2008-01-01
Marine and freshwater mussels are notorious foulers of natural and manmade surfaces, secreting specialized protein adhesives for rapid and durable attachment to wet substrates. Given the strong and water-resistant nature of mussel adhesive proteins, significant potential exists for mimicking their adhesive characteristics in bioinspired synthetic polymer materials. An important component of these proteins is L-3,4-dihydroxylphenylalanine (DOPA), an amino acid believed to contribute to mussel glue solidification through oxidation and crosslinking reactions. Synthetic polymers containing DOPA residues have previously been shown to crosslink into hydrogels upon the introduction of oxidizing reagents. Here we introduce a strategy for stimuli responsive gel formation of mussel adhesive protein mimetic polymers. Lipid vesicles with a bilayer melting transition of 37 °C were designed from a mixture of dipalmitoyl and dimyristoyl phosphatidylcholines and exploited for the release of a sequestered oxidizing reagent upon heating from ambient to physiologic temperature. Colorimetric studies indicated that sodium-periodate-loaded liposomes released their cargo at the phase transition temperature, and when used in conjunction with a DOPA-functionalized poly(ethylene glycol) polymer gave rise to rapid solidification of a crosslinked polymer hydrogel. The tissue adhesive properties of this biomimetic system were determined by in situ thermal gelation of liposome/polymer hydrogel between two porcine dermal tissue surfaces. Bond strength measurements showed that the bond formed by the adhesive hydrogel (mean = 35.1 kPa, SD = 12.5 kPa, n = 11) was several times stronger than a fibrin glue control tested under the same conditions. The results suggest a possible use of this biomimetic strategy for repair of soft tissues. PMID:18458476
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rong Jiang Yan; Yunxia Luo; Bingzheng Jiang
1993-02-05
Shrinkage, retractive stress, and infrared dichroism of the drawn low-density polyethylene (LDPE) as-drawn and irradiated by [sup 60]Co-ray have been measured under different annealing conditions. The shrinkage and the disorientation of the irradiated sample was undergone more rapidly than that of unirradiated one as the temperature was continuously increased, surpassing a certain value, and a higher degree of shrinkage and disorientation was achieved finally for the irradiated sample when the samples were annealed with free ends. For the samples heated isothermally with fixed ends, the retractive stress went through a maximum and then attenuated to a limited value, and themore » degree of such a stress attenuation for the unirradiated sample was much more than that for the irradiated sample. These results show that the taut tie molecules (TTMs) in drawn PE can relax by the pulling of chain segments out of crystal blocks that they anchored in at elevated temperatures higher than the [alpha] transition and also by the displacing of microfibrils if the samples were annealed with free ends. The cross-links produced by irradiation prohibit the former process. It was further observed that the dependence of the average extinction coefficient of the band at 2,016 cm[sup [minus]1] on that of the band at 1,894 cm[sup [minus]1] is related to irradiation and annealing conditions, which has also been explained by the relaxation of TTMs and the function of irradiation-induced cross-linking on the relaxation.« less
Differential Regulation of Angiogenesis using Degradable VEGF-Binding Microspheres
Belair, David G.; Miller, Michael J.; Wang, Shoujian; Darjatmokon, Soesiawati R.; Binder, Bernard Y.K.; Sheibani, Nader; Murphy, William L.
2016-01-01
Vascular endothelial growth factor (VEGF) spatial and temporal activity must be tightly controlled during angiogenesis to form perfusable vasculature in a healing wound. The native extracellular matrix (ECM) regulates growth factor activity locally via sequestering, and researchers have used ECM-mimicking approaches to regulate the activity of VEGF in cell culture and in vivo. However, the impact of dynamic, affinity-mediated growth factor sequestering has not been explored in detail with biomaterials. Here, we sought to modulate VEGF activity dynamically over time using poly(ethylene glycol) microspheres containing VEGF-binding peptides (VBPs) and exhibiting varying degradation rates. The degradation rate of VBP microspheres conferred a differential ability to up- or down-regulate VEGF activity in culture with primary human endothelial cells. VBP microspheres with fast-degrading crosslinks reduced VEGF activity and signaling, while VBP microspheres with no inherent degradability sequestered and promoted VEGF activity in culture with endothelial cells. VBP microspheres with degradable crosslinks significantly reduced neovascularization in vivo, but neither non-degradable VBP microspheres nor bolus delivery of soluble VBP reduced neovascularization. The covalent incorporation of VBP to degradable microspheres was required to reduce neovascularization in a mouse model of choroidal neovascularization in vivo, which demonstrates a potential clinical application of degradable VBP microspheres to reduce pathological angiogenesis. The results herein highlight the ability to modulate the activity of a sequestered growth factor by changing the crosslinker identity within PEG hydrogel microspheres. The insights gained here may instruct the design and translation of affinity-based growth factor sequestering biomaterials for regenerative medicine applications. PMID:27061268
Analysis of strategies to increase external fixator stiffness: is double stacking worth the cost?
Strebe, Sara; Kim, Hyunchul; Russell, Joseph P; Hsieh, Adam H; Nascone, Jason; O'Toole, Robert V
2014-07-01
We compared the mechanical benefits and costs of 3 strategies that are commonly used to increase knee-spanning external fixator stiffness (resistance to deformation): double stacking, cross-linking, and use of an oblique pin. At our academic trauma centre and biomechanical testing laboratory, we used ultra-high-molecular-weight polyethylene bone models and commercially available external fixator components to simulate knee-spanning external fixation. The models were tested in anterior-posterior bending, medial-lateral bending, axial compression, and torsion. We recorded the construct stiffness for each strategy in all loading modes and assessed a secondary outcome of cost per 10% increase in stiffness. Double stacking significantly increased construct stiffness under anterior-posterior bending (109%), medial-lateral bending (22%), axial compression (150%), and torsion (41%) (p<0.05). Use of an oblique pin significantly increased stiffness under torsion (25%) (p<0.006). Cross-linking significantly increased stiffness only under torsion (29%) (p<0.002). Double stacking increased costs by 84%, cross-linking by 28%, and use of an oblique pin by 15% relative to a standard fixator. All 3 strategies increased stiffness under torsion to varying degrees, but only double stacking increased stiffness in all 4 testing modalities (p<0.05). Double stacking is most effective in increasing resistance to bending, particularly under anterior-posterior bending and axial compression, but requires a relatively high cost increase. Clinicians can use these data to help guide the most cost-effective strategy to increase construct stiffness based on the plane in which stiffness is needed. Copyright © 2013 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Boukezzi, L.; Rondot, S.; Jbara, O.; Boubakeur, A.
2017-03-01
Thermal aging of cross-linked polyethylene (XLPE) can cause serious concerns in the safety operation in high voltage system. To get a more detailed picture on the effect of thermal aging on the trapping and detrapping process of XLPE in the melting temperature range, Thermal Stimulated Current (TSC) have been implemented in a Scanning Electron Microscope (SEM) with a specific arrangement. The XLPE specimens are molded and aged at two temperatures (120 °C and 140 °C) situated close to the melting temperature of the material. The use of SEM allows us to measure both leakage and displacement currents induced in samples under electron irradiation. The first represents the conduction process of XLPE and the second gives information on the trapping of charges in the bulk of the material. TSC associated to the SEM leads to show spectra of XLPE discharge under thermal stimulation using both currents measured after electron irradiation. It was found that leakage current in the charging process may be related to the physical defects resulting in crystallinity variation under thermal aging. However the trapped charge can be affected by the carbonyl groups resulting from the thermo-oxidation degradation and the disorder in the material. It is evidenced from the TSC spectra of unaged XLPE that there is no detrapping charge under heat stimulation. Whereas the presence of peaks in the TSC spectra of thermally aged samples indicates that there is some amount of trapped charge released by heating. The detrapping behavior of aged XLPE is supported by the supposition of the existence of two trap levels: shallow traps and deep traps. Overall, physico-chemical reactions under thermal aging at high temperatures leads to the enhancement of shallow traps density and changes in range of traps depth. These changes induce degradation of electrical properties of XLPE.
Hoor, Azadeh; Rowe, R Kerry
2012-05-01
Heat generated by the biodegradation of waste and other chemical processes in a landfill can potentially affect the long-term performance of landfill liner system, in particular that of a high-density polyethylene geomembrane. In a double liner system, the difference in leachate exposure and temperature might improve the long-term performance of the secondary geomembrane compared to that of the primary geomembrane. However, in some cases, the temperature is likely to be high enough to substantially reduce the service-life of the secondary geomembrane. This study explores the possible effectiveness of using tire chips as thermal insulation between primary and secondary liners to reduce the temperature of secondary geomembranes as compared to traditional soil materials. Heat and contaminant migration analyses are performed for cases with no insulation and for cases in which a layer of soil or tire chips has been used as thermal insulation between the primary and secondary liners. The effect of insulation on prolonging the service-life of a secondary geomembrane and, consequently, on contaminant transport through a liner system is examined for the case of a volatile organic compound (dichloromethane) found in landfill leachate. The study suggests that the use of tire chips warrants consideration, however there are other practical issues that require consideration in the detailed design and construction of landfill liners. Issues such as finite service-life, low working temperature, excessive settlement, ability to generate internal heat, leaching of tire chips and limitations in performing electrical resistivity leak detection tests are identified. Copyright © 2012 Elsevier Ltd. All rights reserved.
Tribology of total hip arthroplasty prostheses
Rieker, Claude B.
2016-01-01
Articulating components should minimise the generation of wear particles in order to optimize long-term survival of the prosthesis. A good understanding of tribological properties helps the orthopaedic surgeon to choose the most suitable bearing for each individual patient. Conventional and highly cross-linked polyethylene articulating either with metal or ceramic, ceramic-on-ceramic and metal-on-metal are the most commonly used bearing combinations. All combinations of bearing surface have their advantages and disadvantages. An appraisal of the individual patient’s objectives should be part of the assessment of the best bearing surface. Cite this article: Rieker CB. Tribology of total hip arthroplasty prostheses: what an orthopaedic surgeon should know. EFORT Open Rev 2016;1:52-57. DOI: 10.1302/2058-5241.1.000004. PMID:28461928
Allabashi, Roza; Arkas, Michael; Hörmann, Gerold; Tsiourvas, Dimitris
2007-01-01
Triethoxysilylated derivatives of poly(propylene imine) dendrimer, polyethylene imine and polyglycerol hyperbranched polymers and beta-cyclodextrin have been synthesized and characterized. These compounds impregnated ceramic membranes made from Al(2)O(3), SiC and TiO(2) and subsequently sol-gel reaction led to their polymerization and chemical bond formation with the ceramic substrates. The resulting organic-inorganic filters were tested for the removal of a variety of organic pollutants from water. They were found to remove of polycyclic aromatic hydrocarbons (up to 99%), of monocyclic aromatic hydrocarbons (up to 93%), trihalogen methanes (up to 81%), pesticides (up to 43%) and methyl-tert-butyl ether (up to 46%).
Peptide-Appended Permethylated β-Cyclodextrins with Hydrophilic and Hydrophobic Spacers
2017-01-01
A novel synthetic methodology, employing a combination of the strain-promoted azide–alkyne cycloaddition and maleimide–thiol reactions, for the preparation of permethylated β-cyclodextrin-linker-peptidyl conjugates is reported. Two different bifunctional maleimide cross-linking probes, the polyethylene glycol containing hydrophilic linker bicyclo[6.1.0] nonyne-maleimide and the hydrophobic 5′-dibenzoazacyclooctyne-maleimide, were attached to azide-appended permethylated β-cyclodextrin. The successfully introduced maleimide function was exploited to covalently graft a cysteine-containing peptide (Ac-Tyr-Arg-Cys-Amide) to produce the target conjugates. The final target compounds were isolated in high purity after purification by isocratic preparative reverse-phase high-performance liquid chromatography. This novel synthetic approach is expected to give access to many different cyclodextrin–linker peptides. PMID:28697600
High-performance flexible microwave passives on plastic
NASA Astrophysics Data System (ADS)
Ma, Zhenqiang; Seo, Jung-Hun; Cho, Sang June; Zhou, Weidong
2014-06-01
We report the demonstration of bendable inductors, capacitors and switches fabricated on a polyethylene terephthalate (PET) substrate that can operate at high microwave frequencies. By employing bendable dielectric and single crystalline semiconductor materials, spiral inductors and metal-insulator-metal (MIM) capacitors with high quality factors and high resonance frequencies and single-pole, single-throw (SPST) switches were archived. The effects of mechanical bending on the performance of inductors, capacitors and switches were also measured and analyzed. We further investigated the highest possible resonance frequencies and quality factors of inductors and capacitors and, high frequency responses and insertion loss. These demonstrations will lead to flexible radio-frequency and microwave systems in the future.
Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures
Pekala, R.W.
1998-04-28
The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes {<=}1000 {angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.
Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures
Pekala, Richard W.
1998-04-28
The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes .ltoreq.1000 .ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.
Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures
Pekala, Richard W.
1995-01-01
The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes.ltoreq.1000.ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.
Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures
Pekala, R.W.
1995-12-19
The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes{<=}1000{angstrom}, and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050 C to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors. 8 figs.
Organic aerogels from the sol-gel polymerization of phenolic-furfural mixtures
Pekala, Richard W.
1996-01-01
The sol-gel polymerization of a phenolic-furfural mixture in dilute solution leads to a highly cross-linked network that can be supercritically dried to form a high surface area foam. These porous materials have cell/pore sizes .ltoreq.1000.ANG., and although they are dark brown in color, they can be classified as a new type of aerogel. The phenolic-furfural aerogel can be pyrolyzed in an inert atmosphere at 1050.degree. C. to produce carbon aerogels. This new aerogel may be used for thermal insulation, chromatographic packing, water filtration, ion-exchange, and carbon electrodes for energy storage devices, such as batteries and double-layer capacitors.
The role of inserted polymers in polymeric insulation materials: insights from QM/MD simulations.
Li, Chunyang; Zhao, Hong; Zhang, Hui; Wang, Ying; Wu, Zhijian; Han, Baozhong
2018-02-28
In this study, we performed a quantum chemical molecular dynamics (QM/MD) simulation to investigate the space charge accumulation process in copolymers of polyethylene (PE) with ethylene acrylic acid (EAA), ethylene vinyl acetate (EVA), styrene-ethylene-butadiene-styrene (SEBS), and black carbon (BC). We predicted that BC, especially branched BC, would possess the highest electron affinity and is identified as the most promising filler in power cable insulation. Following incorporations of 0-4 high-energy electrons into the composites, branched BC exhibited the highest stability and almost all electrons were trapped by it. Therefore, PE was protected efficiently and BC can be considered as an efficient filler for high voltage cables and an inhibitor of tree formation. On the contrary, although EAA, EVA, and SEBS can trap high-energy electrons, the latter can be supersaturated in composites of EAA, EVA, and SEBS with PE. The inserted polymers was unavoidably destroyed following C-H and C-O bond cleavage, which results from the interactions and charge transfer between PE and inserted polymers. The content effects of -COOH, benzene, and -OCOCH 3 groups on the electron trapping, mobility and stability of PE were also investigated systematically. We hope this knowledge gained from this work will be helpful in understanding the role of inserted polymers and the growth mechanisms of electrical treeing in high voltage cable insulation.
Biswas, Kaushik; Abhari, Ramin
2014-10-03
A promising approach to increasing the energy efficiency of buildings is the implementation of a phase change material (PCM) in the building envelope. Numerous studies over the last two decades have reported the energy saving potential of PCMs in building envelopes, but their wide application has been inhibited, in part, by their high cost. This article describes a novel PCM made of naturally occurring fatty acids/glycerides trapped into high density polyethylene (HDPE) pellets and its performance in a building envelope application. The PCM-HDPE pellets were mixed with cellulose insulation and then added to an exterior wall of a test buildingmore » in a hot and humid climate, and tested over a period of several months, To demonstrate the efficacy of the PCM-enhanced cellulose insulation in reducing the building envelope heat gains and losses, side-by-side comparison was performed with another wall section filled with cellulose-only insulation. Further, numerical modeling of the test wall was performed to determine the actual impact of the PCM-HDPE pellets on wall-generated heating and cooling loads and the associated electricity consumption. The model was first validated using experimental data and then used for annual simulations using typical meteorological year (TMY3) weather data. Furthermore, this article presents the experimental data and numerical analyses showing the energy-saving potential of the new PCM.« less
Progress in Characterizing Thermal Degradation of Ethylene-Propylene Rubber
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fifield, Leonard S.; Huang, Qian; Childers, Matthew I.
Ethylene-propylene rubber (EPR) is one of the two most common nuclear cable insulation materials. A large fraction of EPR-insulated cables in use in the nuclear industry were manufactured by The Okonite Company. Okoguard® is the name of the medium voltage thermoset EPR manufactured by The Okonite Company. Okoguard® has been produced with silane-treated clay filler and the characteristic pink color since the 1970’s. EPR is complex material that undergoes simultaneous reactions during thermal aging including oxidative and thermal cleavage and oxidative and thermal crosslinking. This reaction complexity makes precise EPR service life prediction from accelerated aging using approaches designed formore » single discreet reactions such as the Arrhenius approach problematic. Performance data and activation energies for EPR aged at conditions closer to service conditions will improve EPR lifetime prediction. In this report pink Okoguard® EPR insulation material has been thermally aged at elevated temperatures. A variety of characterization techniques have been employed to track material changes with aging. It was noted that EPR aged significant departure in aging behavior seemed to occur at accelerated aging temperatures between 140°C and 150°C at around 20 days of exposure. This may be due to alternative degradation mechanisms being accessed at this higher temperature and reinforces the need to perform accelerated aging for Okoguard® EPR service life prediction at temperatures below 150°C.« less
Clay Nanocomposite/Aerogel Sandwich Structures for Cryotanks
NASA Technical Reports Server (NTRS)
Miller, Sandi; Leventis, Nicholas; Johnston, J. Chris; Meador, Michael
2006-01-01
GRC research has led to the development of epoxy-clay nanocomposites with 60-70% lower gas permeability than the base epoxy resin. Filament wound carbon fiber reinforced tanks made with this nanocomposite had a five-fold lower helium leak rate than the corresponding tanks made without clay. More recent work has produced new composites with more than a 100-fold reduction in helium permeability. Use of these advanced, high barrier composites would eliminate the need for a liner in composite cryotanks, thereby simplifying construction and reducing propellant leakage. Aerogels are attractive materials for use as cryotank insulation because of their low density and low thermal conductivity. However, aerogels are fragile and have poor environmental stability, which have limited their use to certain applications in specialized environments (e.g., in certain types of nuclear reactors as Cerenkov radiation detectors, and as thermal insulators aboard space rovers on Mars). New GRC developed polymer crosslinked aerogels (X-Aerogels) retain the low density of conventional aerogels, but they demonstrate a 300-fold increase in their mechanical strength. Currently, our strongest materials combine a density of approx. 0.45 g/cc, a thermal conductivity of approx. 0.04 W/mK and a compressive strength of 185 MPa. Use of these novel aerogels as insulation materials/structural components in combination with the low permeability of epoxy-clay nanocomposites could significantly reduce cryotank weight and improve durability.
Surface layer modification of ion bombarded HDPE
NASA Astrophysics Data System (ADS)
Bielinski, D.; Lipinski, P.; Slusarski, L.; Grams, J.; Paryjczak, T.; Jagielski, J.; Turos, A.; Madi, N. K.
2004-08-01
Press-moulded, high density polyethylene (HDPE) samples were subjected to ion bombardment and effects of the modification studied. He + ions of energy 100 keV or Ar + ions of energy 130 keV were applied in the range of dose 1-30 × 10 15/cm 2 or 1-100 × 10 14/cm 2, respectively. This paper has been focused on structural changes of the surface layer. The consequences of the modification were studied with TOF-SIMS and FTIR-IRS techniques. The results point on two mechanisms taking place simultaneously: ionization of polymer macromolecules and chain scission--resulting in creation of macroradicals. Both of them produce oxidation and lead to significant release of hydrogen. The former diminishes for the highest ion doses, however, creation of molecular oxygen cannot be excluded. The latter in the case of Ar + ion bombardment is reflected by prevailing degradation of the surface layer of HDPE. Contrary to the effect of heavy ions, He + ion bombardment was found to produce significant increase of the material hardness, which was explained by crosslinking of polyethylene. A mechanism of polyacetylene formation, proceeding finally to cross-polymerization of the polymer was proposed. Apart from structural changes, the modification revealed additionally a possibility to improve the wettability of the polymer.