Pu Ratio Research Articles

Plutonium Isotopes (239-241Pu) Dissolved in Pacific Ocean Waters Detected by Accelerator Mass Spectrometry: No Effects of the Fukushima Accident Observed.

The concentration of plutonium (Pu) and the isotopic ratios of 240Pu to 239Pu and 241Pu to 239Pu were determined by accelerator mass spectrometry (AMS) in Pacific Ocean water samples (20 L each) collected in late 2012. The isotopic Pu ratios are important indicators of different contamination sources and were used to identify a possible release of Pu into the ocean by the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident. In particular, 241Pu is a well-suited indicator for a recent entry of Pu because 241Pu from fallout of nuclear weapon testings has already significantly decayed. A total of 10 ocean water samples were prepared at the Radiochemie München of the TUM and analyzed at the Vienna Environmental Research Laboratory (VERA). Several samples showed a slightly elevated 240Pu/239Pu ratio of up to 0.22 ± 0.02 compared to global fallout (240Pu/239Pu = 0.180 ± 0.007), whereas all measured 241Pu-to-239Pu ratios were consistent with nuclear weapon fallout (241Pu/239Pu < 2.4 × 10-3), which means that no impact from the Fukushima accident was detected. From the average 241Pu-to-239Pu ratio of 8-2+3 ×10-4 at a sampling station located at a distance of 39.6 km to FDNPP, the 1-σ upper limit for the FDNPP contribution to the 239Pu inventory in the water column was estimated to be 0.2%. Pu, with the signature of weapon-grade Pu was found in a single sample collected around 770 km off the west coast of the United States.

Accurate purification age determination of individual uranium-plutonium mixed particles.

Age of individual uranium-plutonium (U/Pu) mixed particles with various U/Pu atomic ratios (1-70) were determined by inductively coupled plasma mass spectrometry. Micron-sized particles were prepared from U and Pu certified reference materials. The Pu reference was stored for 4-6 years since the last purification (July 14, 2008). The Pu purification age was obtained from the (241)Am/(241)Pu ratio which was calculated from the product of three measured ratios of Pu and Am isotopes in the eluted fractions. These ratios were measured by a high-resolution inductively coupled plasma mass spectrometer equipped with a desolvation system. Femto-gram to pico-gram quantities of Am, U, and Pu in a sample solution were sequentially separated on a small anion-exchange column. The (241)Am/(241)Pu ratio was accurately determined by spiking pure (243)Am into the sample solution. The average determined age for the particles for the five independent U/Pu ratios was in good agreement with the expected age with high accuracy (difference age 0.27 years) and high precision (standard deviation 0.44 years). The described analytical technique can serve as an effective tool for nuclear safeguards and environmental radiochemistry. Figure Young (4-6 y) Pu purification age of individual U/Pu mixed micron-sized reference particles for the five independent U/Pu ratios (1-70) were determined with 0.27±0.44 y difference from the expected age. Sub pico-gram quantities of Am, U and Pu were sequentially separated a small column, and their isotope ratios were accurately measured using an ICP-MS by applying the (243)Am spiking technique to the analysis and correcting the impurity and the contaminations.

236U and 239,240Pu ratios from soils around an Australian nuclear weapons test site

The isotopes 236U, 239Pu and 240Pu are present in surface soils as a result of global fallout from nuclear weapons tests carried out in the 1950's and 1960's. These isotopes potentially constitute artificial tracers of recent soil erosion and sediment movement. Only Accelerator Mass Spectrometry has the requisite sensitivity to measure all three isotopes at these environmental levels. Coupled with its relatively high throughput capabilities, this makes it feasible to conduct studies of erosion across the geographical extent of the Australian continent.In the Australian context, however, global fallout is not the only source of these isotopes. As part of its weapons development program the United Kingdom carried out a series of atmospheric and surface nuclear weapons tests at Maralinga, South Australia in 1956 and 1957. The tests have made a significant contribution to the Pu isotopic abundances present in the region around Maralinga and out to distances ∼1000 km, and impact on the assessment techniques used in the soil and sediment tracer studies. Quantification of the relative fallout contribution derived from detonations at Maralinga is complicated owing to significant contamination around the test site from numerous nuclear weapons safety trials that were also carried out around the site. We show that 236U can provide new information on the component of the fallout that is derived from the local nuclear weapons tests, and highlight the potential of 236U as a new fallout tracer.

The plutonium–oxygen phase diagram in the 25–900 °C range: Non-existence of the PuO1.515 phase

Evaluation of data for phases formed in the Pu–O system at temperatures below 900°C shows that the observed oxides are not at equilibrium. Results are consistent with coexistence of a hexagonal solid solution (hex-PuO1.5+z, 0⩽z⩽0.010) and a cubic phase (cub-PuO1.60) in equilibrium at 800°C, but fail to confirm that the O/Pu ratio of the body-centered-cubic (bcc) oxide formed near the sesquioxide composition is 1.515 (1.52) or that bcc-PuO1.515 is formed by the peritectic reaction of hex-PuO1.510 with cub-PuO1.60. Stable Pu(IV)/Pu(III) ratios observed for products of the Pu–H2O reaction correspond to members of the PunO2n−2 homologous series, but a product is not formed at O/Pu=1.515. Metastable bcc-PuO1.50 (n=4) and stable hex-PuO1.5+z coexist below 285°C, the point at which reversible eutectic decomposition of cubic PuO1.60 (n=5) produces a non-equilibrium mixture of bcc-PuO1.50 and sub-stoichiometric dioxide (PuO2−y). Transformation of bcc-PuO1.50 to stable hex-PuO1.50 and reactions of the hexagonal oxide to form higher-composition cubic phases are kinetically hindered. An alternative diagram describing non-equilibrium chemical behavior of the Pu–O system is presented.

Using Isotopic Ratios for Discrimination of Environmental Anthropogenic Radioactivity

When air is pulled into the WIPP repository for ventilation purposes, this air is unfiltered and contains all the components of ubiquitous anthropogenic radionuclides from global nuclear fallout (including Cs and Pu isotopes). Although the NORM in aeolian sand and dust contribute to the gross alpha beta activity on effluent air filters, there remains a need to discriminate effluent TRU generated in the disposal process at WIPP from TRU being pulled into the repository with the unfiltered surface air. This is only evaluated using ratios of Cs and Pu activity found through radioassay of air filters taken from the mine effluent. By characterizing both the credible range of Cs/Pu ratios from the environment and those known to exist in the waste, a rigorous test criteria is attained. The use of HPGE to assay Cs in the intake dust plated out in the mine allowed a gross assay of total TRU radioactivity pulled into the mine over time from global fallout. Radiochemistry of samples from deposition in the mine's air intake shaft was also carried out. The use of net activity ratios at background levels is also shown to follow a Cauchy distribution in terms of their expected statistical distributions.

Molecular dynamic study on thermal expansion of U1-xPuxO2

Molecular dynamic simulation is performed to investigate the thermal properties of U1-xPuxO2 (x=0.07, 0.15, 0.25, 0.5) using the potential of partially ionic model at temperatures ranging from 300 to 3000 K and pressures in a range of 0-1.5 GPa. The results indicate that the lattice parameters decrease linearly with Pu ratio increasing under different temperatures. The linear expansion coefficient increases with Pu ratio increasing. The isothermal compressibility decreases with Pu ratio decreasing. In addition, the experience functions of lattice parameter and linear expansion coefficient are also derived.

LA-ICP-MS for Pu source identification at Mayak PA, the Urals, Russia

Information on Pu in environmental samples is traditionally based on the determination of the (240+239)Pu activity via Alpha Spectrometry (AS). A large number of alpha spectrometry sources (planchettes) containing radiochemically separated Pu are therefore stored worldwide and are available for further analyses. These archive samples represent a resource from which valuable information on isotopic composition of alpha emitters including Pu can be obtained. The relative abundances of Pu isotopes can be used to trace specific Pu sources and characterize the relative contributions of different Pu sources in a sample. Thus, in addition to the total (239+240)Pu activity, determination of the (240)Pu/(239)Pu ratio can provide valuable information on the nature of the Pu emitting sources. The Pu isotopic ratios can be determined by mass spectrometry techniques such as Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICPMS) or Accelerator Mass Spectrometry (AMS) that require dissolution and complete destruction of the material deposited on the planchettes. In this study Laser Ablation (LA)-quadrupole-ICP-MS has been employed for the analysis of (239)Pu/(240)Pu ratios from alpha-planchettes prepared from samples originating from the Mayak PA nuclear facility, Russia. The results are compared with data from AMS and show that the (240)Pu/(239)Pu ratios obtained by LA-ICP-MS can be utilized to distinguish weapons-grade Pu from civil reprocessing sources. Moreover, isotope ratio mapping can also be performed across the planchettes, allowing e.g. the visualization of possible inhomogeneities in the Pu-isotope distribution on their surface. Thus, this solid sample technique can be applied to extract additional information from existing archives of samples.

Measurements of 236U in Ancient and Modern Peat Samples and Implications for Postdepositional Migration of Fallout Radionuclides

(236)U was analyzed in an ombrotrophic peat core representing the last 80 years of atmospheric deposition and a minerotrophic peat sample from the last interglacial period. The determination of (236)U at levels of 10(7) atoms/g was possible by using ultraclean laboratory procedures and accelerator mass spectrometry. The vertical profile of the (236)U/(238)U isotopic ratio along the ombrotrophic peat core represents the first observation of the (236)U bomb peak in a terrestrial environment. A constant level of anthropogenic (236)U with an average (236)U/(238)U isotopic ratio of (1.24 ± 0.08) × 10(-6) in the top layers of the core was observed. Comparing the abundances of the global fallout derived (236)U and (239)Pu along the peat core, the post depositional migration of plutonium clearly exceeds that of uranium. However, the cumulative (236)U/(239)Pu ratio of 0.62 ± 0.31 is in agreement with previous studies on the global fallout uranium and plutonium. In the interglacial peat samples a (236)U/(238)U isotopic ratio of (3.3 ± 0.7) × 10(-12) was detected; although this measurement is an upper limit, it constitutes a significant step forward in the experimental determination of the natural (236)U abundance and represents a true background sample for the ombrotrophic peat core.

Solubility of hot fuel particles from Chernobyl—Influencing parameters for individual radiation dose calculations

Nuclear fuel particles of Chernobyl origin are carriers of increased radioactivity (hot particles) and are still present in the atmosphere of the Chernobyl exclusion zone. Workers in the zone may inhale these particles, which makes assessment necessary. The residence time in the lungs and the transfer in the blood of the inhaled radionuclides are crucial for inhalation dose assessment. Therefore, the dissolution of several kinds of nuclear fuel particles from air filters sampled in the Chernobyl exclusion zone was studied. For this purpose filter fragments with hot particles were submersed in simulated lung fluids (SLFs). The activities of the radionuclides 137Cs, 90Sr, 239+240Pu and 241Am were measured in the SLF and in the residuum of the fragments by radiometric methods after chemical treatment. Soluble fractions as well as dissolution rates of the nuclides were determined. The influence of the genesis of the hot particles, represented by the 137Cs/239+240Pu ratio, on the availability of 137Cs was demonstrated, whereas the dissolution of 90Sr, 239+240Pu and 241Am proved to be independent of genesis. No difference in the dissolution of 137Cs and 239+240Pu was observed for the two applied types of SLF. Increased solubility was found for smaller hot particles. A two-component exponential model was used to describe the dissolution of the nuclides as a function of time. The results were applied for determining individual inhalation dose coefficients for the workers at the Chernobyl construction site. Greater dose coefficients for the respiratory tract and smaller coefficients for the other organs were calculated (compared to ICRP default values). The effective doses were in general lower for the considered radionuclides, for 241Am even by one order of magnitude.

Determination of 239Pu, 240Pu, 241Pu and 242Pu at femtogram and attogram levels – evidence for the migration of fallout plutonium in an ombrotrophic peat bog profile

The isotopic composition of plutonium ((239)Pu, (240)Pu, (241)Pu and (242)Pu) was investigated in a ∼0.5 m long peat core from an ombrotrophic bog (Black Forest, Germany) using clean room procedures and accelerator mass spectrometry (AMS). This sophisticated analytical approach was ultimately needed to detect reliably the Pu concentrations present in the peat samples at femtogram (fg) and attogram (ag) levels. The mean (240)Pu/(239)Pu isotopic ratio of 0.19 ± 0.02 (N = 32) in the peat layers, representing approximately the last 80 years, was in good agreement with the accepted value of 0.18 for the global fallout in the Northern Hemisphere. This finding is largely supported by the corresponding and rather constant (241)Pu/(239)Pu (0.0012 ± 0.0005) and (242)Pu/(239)Pu (0.004 ± 0.001) ratios. Since the Pu isotopic composition characteristic of the global fallout was also identified in peat samples pre-dating the period of atmospheric atom bomb testing (AD 1956-AD 1980), migration of Pu within the peat profile is clearly indicated. These results highlight, for the first time, the mobility of Pu in a peat bog with implications for the migration of Pu in other acidic, organic rich environments such as forest soils and other wetland types. These findings constitute a direct observation of the behaviour of Pu at fg and ag levels in the environment. The AMS measurements of Pu concentrations (referring to a corresponding activity of (240+239)Pu from 0.07 mBq g(-1) to 5 mBq g(-1)) essentially confirm our a priori estimates based on existing (241)Am and (137)Cs data in the investigated peat core and agree well with the global fallout levels from the literature. Exclusively employing the Pu isotope ratios established for the peat samples, the date of the Pu irradiation (AD 1956, correctable to AD 1964) was calculated and subsequently compared to the (210)Pb age of the peat layers; this comparison provided an additional hint that global fallout derived Pu is not fixed in the peat column, but has migrated downwards along the peat profile to layers preceding the nuclear age.

Measurements of low-level anthropogenic radionuclides from soils around Maralinga

The isotopes 239 Pu and 240 Pu are present in surface soils as a result of global fallout from nuclear weapons tests carried out in the 1950's and 1960's. These isotopes constitute artificial tracers of recent soil erosion and sediment movement. In practice the high throughput capabilities and high sensitivity of the AMS technique makes the study of Australia's geographically large areas viable using Pu isotopes. As part of its weapons development program the United Kingdom carried out a series of atmospheric and surface nuclear weapons tests at Maralinga, South Australia in 1956 and 1957. The contribution from the Maralinga tests to the Pu isotopic abundances present in the region around Maralinga is largely unknown. In global fallout, for example, the 240 Pu/ 239 Pu ratio is typically in the range 0.17 - 0.19, but the influence of the regional tests could lead to values outside this range. This would impact on the assessment techniques used in the soil and sediment tracer studies. We report recent measurements on soil samples collected from across the Maralinga Test site.

Verification of a Simple Procedure to Simulate Solvent Extraction by Pulsed Columns

A simple procedure to simulate the important kinetic features of counter-current processes in pulsed columns has been developed. The overall mass transfer coefficient was simplified to be constant along the column, and the stripping of Pu4+ by hydroxylamine is assumed to be instantaneous to avoid complex reaction rate calculations. The number of calculation cells can be determined by making calculations with an increasing number of cells until its influence becomes small enough. The validity of these simplifications was confirmed by comparing the calculation results with a wide range of measured data from extraction and stripping as well as Pu partition tests with laboratory, engineering, and pilot scale columns. This procedure is intended for use in a conceptual design study of a future fast breeder reactor (FBR) reprocessing plant. An example of its application in a flow sheet calculation was demonstrated, where a coextraction process of U and Pu was simulated to find the conditions to obtain a solution with Pu/(U + Pu) ratio being 30% from a typical feed of FBR spent fuel solution.

Interstitial Incorporation of Plutonium into a Low-Dimensional Potassium Borate

The molten boric acid flux reaction of PuBr(3) with KBO(2) at 200 °C results in the formation of large light-yellow crystals of K[B(5)O(7)(OH)(2)]·H(2)O:Pu(4+). Single-crystal X-ray diffraction experiments on the Pu-doped K[B(5)O(7)(OH)(2)]·H(2)O demonstrate two features: (1) K[B(5)O(7)(OH)(2)]·H(2)O:Pu(4+) adopts a one-dimensional borate chain structure with void spaces between the chains. (2) The doping plutonium atoms do not reside on the potassium sites. The latter are not fully occupied. Both laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and energy-dispersive spectrometry analyses indicate that plutonium atoms are uniformly distributed in crystals of K[B(5)O(7)(OH)(2)]·H(2)O with an atomic K:Pu ratio of approximately 65:1 measured by LA-ICP-MS. UV-vis-NIR spectra taken from both freshly made and one day old crystals show that the plutonium present within the crystals is predominantly characterized by Pu(IV). A small amount of Pu(III) is also present initially, but slowly oxidized to Pu(IV) via interaction with oxygen in the air. X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopic measurements confirm that plutonium is mainly present as a form similar to that of a PuO(2) cluster. The combined results suggest that the clusters containing Pu(IV) ions are uniformly distributed in the void spaces between the borate chains.

Chemorheology and thermomechanical characteristics of benzoxazine‐urethane copolymers

AbstractIn this research, processability and some important thermomechanical properties of polybenzoxazine (BA‐a) modified with a highly flexible urethane elastomer (PU) are discussed. This copolymer has been reported to show synergy in its glass transition temperature and some mechanical properties thus provides a fascinating group of high temperature polymers with enhanced flexibility. The results reveal that a processing window of the BA‐a/PU mixtures is widened with the increasing urethane prepolymer fraction, that is, the liquefying temperature is lowered and the gel point shifted to higher temperature with the amount of the PU. Synergism in glass transition temperature (Tg) of this copolymer was clearly confirmed, i.e., Tg's of the BA‐a/PU alloys were significantly greater than those of the parent resins, i.e., BA‐a (Tg = 166°C) and PU (Tg = − 70°C). In addition, flexural modulus was found to systemically decrease from 5.4 GPa of the neat polybenzoxazine to 2.1 GPa at 40% by weight of the PU. Flexural strength of the alloys also shows a synergistic behavior at the BA‐a/PU ratio of 90/10. Coefficient of thermal expansion of the polymer alloys were also found to show a minimum value at BA‐a/PU = 90/10. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Comparative study of fast critical burner reactors and subcritical accelerator driven systems and the impact on transuranics inventory in a regional fuel cycle

In the frame of Partitioning and Transmutation (P&T) strategies, many solutions have been proposed in order to burn transuranics (TRU) discharged from conventional thermal reactors in fast reactor systems. This is due to the favourable feature of neutron fission to capture cross section ratio in a fast neutron spectrum for most TRU. However the majority of studies performed use the Accelerator Driven Systems (ADS), due to their potential flexibility to utilize various fuel types, loaded with significant amounts of TRU having very different Minor Actinides (MA) over Pu ratios. Recently the potential of low conversion ratio critical fast reactors has been rediscovered, with very attractive burning capabilities. In the present paper the burning performances of two systems are directly compared: a sodium cooled critical fast reactor with a low conversion ratio, and the European lead cooled subcritical ADS-EFIT reactor loaded with fertile-free fuel. Comparison is done for characteristics of both the intrinsic core and the regional fuel cycle within a European double-strata scenario. Results of the simulations, obtained by use of French COSI6 code, show comparable performance and confirm that in a double strata fuel cycle the same goals could be achieved by deploying dedicated fast critical or ADS-EFIT type reactors. However the critical fast burner reactor fleet requires ∼30–40% higher installed power then the ADS-EFIT one. Therefore full comparative assessment and ranking can be done only by a parametric sensitivity study of both the fuel cycle and the electricity generating costs.

Sources and distributions of 137Cs, 238Pu, 239,240Pu radionuclides in the north-western Barents Sea

Sediment deposits are the ultimate sink for anthropogenic radionuclides entering the marine environment. The major sources of anthropogenic radionuclides to the Barents Sea are fallout from nuclear weapons tests, long range transport from other seas, and river and non-point freshwater supplies. In this study we investigated activity concentrations, ratios, and inventories of the anthropogenic radionuclides, 137Cs, 238Pu, 239,240Pu in dated sediment cores collected along a north-south transect in the northwestern Barents Sea. The data were used to evaluate the influence of different sources on the derived spatial and temporal patterns of anthropogenic radionuclides in seafloor sediment deposits. Activity concentrations of 137Cs ranged from <0.1 Bq/kg to 10.5 Bq/kg while 239,240Pu ranged from <0.01 Bq/kg to 2.74 Bq/kg and 238Pu activity concentrations ranged from <0.01 Bq/kg to 0.22 Bq/kg. Total inventories of 137Cs ranged from 29.5 ± 1.5 Bq/m 2 to 152.7 ± 5.6 Bq/m 2 and for 239,240Pu inventories (6 sediment layers only) ranged from 9.5 ± 0.3 Bq/m 2 to 29.7 ± 0.4 Bq/m 2. Source contributions varied among stations and between the investigated radionuclides. The 238Pu/ 239,240Pu ratios up to 0.18 indicate discharges from nuclear fuel reprocessing plants as a main contributor of plutonium. Based on 238Pu/ 239,240Pu ratio, it was calculated that up to 19–27% of plutonium is supplied from sources other than atmospheric global fallout. Taking into account Atlantic current flow trajectories and that both activity concentrations and inventories of plutonium negatively correlate with latitude, Sellafield is a major source for the Barents Sea. Concentrations and inventories of 137Cs correlate positively with latitude and negatively with distance from the Svalbard archipelago. The 137Cs concentrations are highest in an area of intensive melting of sea ice formed along the Siberian coast. Thus, sea ice and supplies from Svalbard may be important source of 137Cs to the Barents Sea seafloor.

Isotopic signature of plutonium at Bikini atoll

Atom ratios of the isotopes (239)Pu, (240)Pu, (241)Pu and (244)Pu were determined in sediments and soils from Bikini atoll using low energy Accelerator Mass Spectrometry. All samples had been contaminated by local fallout from nuclear weapon testing between 1946 and 1958 and show significant variations in the isotopic composition, which are ascribed to the different yields of single tests and to the mixture of material from various devices. Differences in the (244)Pu/(239)Pu ratio (2.8-5.7x10(-4)) are more pronounced than in the (240)Pu/(239)Pu ratio of the same samples and provide complementary information to distinguish the sources of contamination.

Thermodynamic Evaluation of Liquid Cd Cathode Containing U and Pu

In our previous study, a mixture of U and Pu was recovered in liquid Cd cathode from molten salt under various conditions of the U:Pu ratio. Two important things were observed. The first was that three kinds of precipitated phase had been detected in the saturated liquid Cd cathode, such as a U metal and two kinds of U-Pu-Cd compound. The compositions of the compounds were roughly (U+Pu):Cd = 1:11 and (U+Pu):Cd = 1:6. The second was that the U metal had selectively precipitated in the saturated liquid Cd cathode under the condition that the U:Pu ratio is higher than about 0.8 in the liquid Cd phase. In the present study, phase diagrams were evaluated by the CALPHAD method on the liquid Cd cathode containing U and Pu. The U-Pu-Cd compounds were modeled as MCd11-type and MCd6-type, respectively, based on the reported binary phase diagrams of U-Cd and Pu-Cd. The calculated result reasonably agreed with the experimental observations. The variations in the U and Pu activities were estimated along with the U:Pu ratio, which is related to the precipitation of various phases in the liquid Cd cathode.

Plutonium AMS measurements in Yangtze River estuary sediment

Abstract The Yangtze River is the largest single source of sediment to the continental shelf of the East China Sea. The quantity of material exported by the river is expected to decrease substantially as a consequence of an extensive continuing program of dam construction within the river catchment. We report here AMS measurements of plutonium isotope concentrations and ratios for selected depth increments from a sediment core, collected from the sub-aqueous delta of the Yangtze River estuary. The Pu derives from atmospheric nuclear weapons testing in the 1950s and 1960s, and is potentially a useful tracer of sediment deposition times in the marine environment. The results show considerable structure in the depth-concentration profile, and offer an excellent opportunity to compare Pu with the more commonly used 137 Cs isotopic tracer. The AMS data show superior sensitivity and indicate that the 240 Pu/ 239 Pu ratio can provide a check on the deposition dates. The changes in the 240 Pu and 239 Pu concentrations and the 240 Pu/ 239 Pu ratios with sediment depth all indicate the possibility of using Pu as a geochronological tool for coastal sediment studies.

Thermomechanical characteristics of benzoxazine–urethane copolymers and their carbon fiber‐reinforced composites

AbstractCopolymers of polybenzoxazine (BA‐a) and urethane elastomer (PU) with three different structures of isocyanates [i.e., toluene diisocyanate (TDI), diphenylmethane diisocyanate, and isophorone diisocyanate], were examined. The experimental results reveal that the enhancement in glass transition temperature (Tg) of BA‐a/PU copolymers was clearly observed [i.e., Tg of the BA‐a/PU copolymers in 60 : 40 BA‐a : PU system for all isocyanate types (Tg beyond 230°C) was higher than those of the parent resins (165°C for BA‐a and −70°C for PU)]. It was reported that the degradation temperature increased from 321°C to about 330°C with increasing urethane content. Furthermore, the flexural strength synergism was found at the BA‐a : PU ratio of 90 : 10 for all types of isocyanates. The effect of urethane prepolymer based on TDI rendered the highest Tg, flexural modulus, and flexural strength of the copolymers among the three isocyanates used. The preferable isocyanate of the binary systems for making high processable carbon fiber composites was based on TDI. The flexural strength of the carbon fiber‐reinforced BA‐a : PU based on TDI at 80 wt % of the fiber in cross‐ply orientation provided relatively high values of about 490 MPa. The flexural modulus slightly decreased from 51 GPa for polybenzoxazine to 48 GPa in the 60 : 40 BA‐a : PU system. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009