The automatic graphitization system (AGE3) by IonPlus is very popular among radiocarbon dating laboratories. Usually, solid samples are burnt in an elemental analyzer (EA), and the gaseous CO2 is transferred for graphitization. Our system is coupled also with an isotope ratio mass spectrometer (IRMS), which measures the δ13C and δ15N of that gas. Some less routine pretreatment protocols require the production of gaseous samples and prevent the possibility of using the EA-AGE3 system, as the EA is used for solid samples only. In order to use that system, including the measurements of stable isotopes, we developed a glass tube cracker that connects to the EA. The device is routinely used in our laboratory and is mainly built from Swaglok catalog parts. We show that the background (blank) levels of a marble standard are indistinguishable between using the cracker and burning solid marble using the EA. We further demonstrate that the δ13C values are consistent and that the extraction efficiency when using the device is above 93%. Full descriptions, drawings, and working protocol are supplied.

We constructed a laser ablation (LA) system using a diode laser for the accelerator mass spectrometry radiocarbon (AMS 14C) measurement of organic materials. The system could extract adequate CO2 to analyze small masses (0.1 mg C) at a resolution of 250 µm by a 5.5 W diode laser. The LA system was assessed using standard materials (IAEA-C1, IAEA-C2, IAEA-C3, IAEA-C6, and Ox II) and applied to natural tree ring samples. For the LA sampling of organic samples, which generally results in incomplete combustion, tungsten (VI) oxide was used as an oxidant to achieve complete burning. The results of the measurement of standard materials showed a low 14C background of F14C 0.0085 ± 0.0005 and reasonable reproduction of 14C values. Finally, we applied this system to a single-year analysis of tree-ringed spruce timber in Alaska. It was observed to have a detectable background for the 14C bomb peak.

Carbon xerogel nanocomposites with integrated Bi and Fe particles (C–Bi–Fe) represent an interesting model of carbon nanostructures decorated with multifunctional nanoparticles (NPs) with applicability for electrochemical sensors and catalysts. The present study addresses the fundamental aspects of the catalyzed growth of nano-graphites in C–Bi–Fe systems, relevant in charge transport and thermo-chemical processes. The thermal evolution of a C–Bi–Fe xerogel is investigated using different pyrolysis treatments. At lower temperatures (~750°C), hybrid bismuth iron oxide (BFO) NPs are frequently observed, while graphitization manifests under more specific conditions such as higher temperatures (~1,050°C) and reduction yields. An in situ heating TEM experiment reveals graphitization activity between 800 and 900°C. NP motion is directly correlated with textural changes of the carbon support due to the catalyzed growth of graphitic nanoshells and nanofibers as confirmed by HR-TEM and electron tomography (ET) for the graphitized sample. An exponential growth model for the catalyst dynamics enables the approximation of activation energies as 0.68 and 0.29–0.34 eV during reduction and graphitization stages. The results suggest some similarities with the tip growth mechanism, while oxygen interference and the limited catalyst–feed gas interactions are considered as the main constraints to enhanced growth.

Medieval manuscripts are invaluable archives of the written history of our past. Manuscripts can be dated and localized paleographically, but this method has its limitations. The Fragmenta membranea manuscript collection at the National Library of Finland has proved difficult to date using paleographic methods. Radiocarbon dating has been applied to manuscripts of parchment before, but a systematic protocol for radiocarbon dating of parchment has not been established with a minimally destructive sampling strategy. In this work, we have established a radiocarbon dating procedure for parchments combining a clean-room based chemical pretreatment process, elemental analyzer combustion, automatic graphitization and accelerator mass spectrometry (AMS) measurements to reduce the AMS target size from a typical 1 mg of carbon. Prolonged acid treatment resulted in improved dating accuracy, since this is consistent with the manufacturing process of medieval parchment involving a lime bath. Two different combustion processes were compared. The traditional closed tube combustion (CTC) method provided a well-established though labor-intensive way to produce 1 mg AMS targets. The Elemental Analyzer-based process (EA-HASE, Elemental Analyzer Helsinki Adaptive Sample prEparation line), is designed for fast combustion and smaller sample sizes. The EA-HASE process was capable of reproducing the simulated radiocarbon ages of known-age samples with AMS graphite target sizes of 0.3 mg of carbon, corresponding to a 3 mm2 area of a typical medieval parchment. The full potential of the process to go down to as little as 50 μg will be further explored in the future in parallel to studies of sample-specific contamination issues.

Graphitization of 0.5–1.5 mg C, and of smaller samples to a lesser extent, is routinely done at our Facility by reduction over zinc. The method yields low background, good accuracy but offers a limited throughput, requires dedicated equipment and considerable operator time. Sealed-tube graphitization is faster, easier and cost-efficient producing as many graphites as CO2 can be purified in one day with low background, good accuracy and precision, provided precise measurements of δ13C values can be attained by accelerator mass spectrometry (AMS) to correct for isotope fractionation (Xu et al. 2007). We tested sealed-tube graphitization on 0.1 to 1.0 mg C samples and found that while we were able to obtain low backgrounds of >57,000 ±1000 yr BP for ∼1.7 mg C and 41,230 ± 430 yr BP for ∼0.09 mg C (0.0008 ± 0.0001 and 0.0059 ± 0.0003 Fraction Modern, respectively), results were variable for sample sizes <0.5 mg C. Measurements of FIRI Belfast Cellulose and TIRI Barleymash showed 0.3–0.6% precision and 1% accuracy for most sample sizes. We found better results in our laboratory by introducing the following modifications: (1) shorter inner tube (2 cm long), (2) short flame-seal length (∼7–8 cm) and (3) keeping the inner tube with iron separate from the outer tube containing zinc and titanium hydride during cleaning.

Metamorphic grade, palaeothermal history and the influence of tectonic strain on clay minerals and organic matter transformation were studied in the eastern part of the Teplá-Barrandian unit in the Czech Republic. The metamorphic grade of pelitic sediments ranges from the lower anchizone (IC ~0.30–0.36Δº2θ) to the lowermost epizone (IC ~0.24–0.26Δº2θ). Increase in metamorphic grade is paralleled by the development of anastomosing cleavage and lenticular quartz grains in the anchizone which give way to slaty cleavage and dynamically recrystallized ribbon quartz grains in the lower epizone. White mica in highly strained rocks generally has greater IC values whereas chlorite displays reduced values in deformed and cleaved samples. The organic matter dispersed in the sediments represents a complex assemblage of highly matured particles of uncertain origin, pyrobitumen and ‘transitional matter’. The reflectance of organic fragments generally varies from 3.1% to 7.7% of Rmax which suggests anthracite to meta-anthracite rank progrades to semigraphite in higher-grade samples, although the overall link between Rmax and IC values is weak, if present at all. Newly formed shear-induced graphite appears abruptly near the anchizone-epizone boundary and correlates with the onset of plastic deformation and dynamic recrystallization of quartz grains in the host sediments.

Maximum metamorphic temperatures within the Neoproterozoic sequence in the range of 250–350ºC were attained during the Cadomian (Pan-African) orogeny at 540–550 Ma. Apatite fission-track analysis reveals a subsequent decrease in rock temperature over the period 340–350 Ma that persisted throughout the late Palaeozoic. The most recent episode of accelerated cooling occurred between 20 and 40 Ma, corresponding with the regional uplift of the Bohemian Massif due to the Alpine orogeny.

The degree of metamorphism affecting the Devonian-Carboniferous rocks of the Palaeozoic Cinco Villas massif has been studied by (a) petrographic techniques, (b) illite crystallinity, and (c) degree of graphitization of the carbonaceous material. Some mineralogical differences have been found between the Devonian and Carboniferous rocks; paragonite and mixed-layer paragonite/muscovite, typical of anchimetamorphic areas, appear in the Devonian but are not found in the Carboniferous rocks. These are characterized by the local appearance of chloritoid, garnet, amphibole, epidote, andalusite and biotite, and the generalized presence of muscovite/chlorite. Illite crystallinity shows a metamorphic zonation (anchizone epizone) towards the granitic Aya massif, and a concentric pattern around the intrusive body.

The optical analysis shows that the first effects of the regional metamorphism began before the D2 deformation, reaching its paroxysm during this phase and continuing afterwards. The degree of graphitization evolves progressively with metamorphism, and this fact is reflected in an exponential relationship between d(002) and crystallinity Lc(002). The similarity in the degree of graphitization between homologous materials within and outside the Aya aureole suggests a similar kinetic factor for both the thermal and regional metamorphisms, or a similar duration time. This fact, as well as the distribution and relationship between the deformation and recrystallization of the minerals, suggests a syn-plutonic regional metamorphism developed at low pressures, in accordance with the value of the b0 parameter for the white micas, and probably a maximum temperature of about 500°C.

A new type of miniaturized, externally heated graphitization reaction furnace, the microconventional furnace (MCF), was constructed following our development of the laser heated furnace (LHF). The MCF is comprised of a gas reactor, a cold finger cooling system, and a compact resistive heater, which can raise the temperature of the hot finger to 850°C. The gas reactor is provided with three integrated valves to connect with the hydrogen/vacuum manifold, to isolate the reactor, and to connect with sample vessels. We made two types of MCF: the type 1 furnace (volume of 0.9 mL), with an integral stainless steel cold finger, and the type 2 furnace (volume from 1.3 to 10 mL), with a changeable glass cold finger. The MCF is designed for above atmospheric pressure (up to 2500 mbar) operation to decrease the overall graphitization time and improve the carbon yield. The MCF provides an effective solution for producing graphite from carbon dioxide (CO2) sample gas from 5 to 2000 µg of carbon with only 0.083 μg of 100 pMC extraneous carbon added. Cross-contamination tests show that the MCFs have no memory effect from previous samples.

New computer-controlled, semi-automatic systems were designed and built for CO2 purification and graphitization at the A.E. Lalonde Accelerator Mass Spectrometry (AMS) Laboratory with consideration for user friendliness and high throughput. The stainless steel vacuum lines are orbitally welded to ensure clean seams with low memory. The insulated graphitization ovens with plug-in electrodes provide a hazard-free environment for operators. The closed-loop cooling system circulating low-viscosity Dynalene at –40°C provides highly efficient water trapping. The LabVIEWTM software features (1) pressure and temperature recording for QA/QC; (2) safety interlocks to preclude operator errors resulting in sample loss, cross-contamination, or damaging a vacuum pump; and (3) automation for leak checking, iron conditioning, and running samples. Results from the first year of routinely measured standards, reference, and background materials are reproducible and within acceptance values. In the first year of operation (commissioned in spring 2014), over 1000 targets (~60% unknowns) were produced. With new tube sealing and CO2 purification lines, and two more graphitization lines now operational, the Lalonde AMS Laboratory is able to provide routine radiocarbon analysis (>200 µg carbon) at a capacity of more than 7000 targets per year. Most importantly, the equipment is safe and intuitive, making it ideal for education and training students to run their own samples.

The Radiocarbon Laboratory of the Universidade Federal Fluminense, in Brazil, has been successfully applying the zinc reduction method for graphitization of carbon samples since the development of its early protocols in 2009. Successive methodological research aiming to improve and, ultimately, optimize the precision and accuracy of our results indicates that graphitization temperatures as low as 460°C promote erratic 13C isotopic fractionation, but an approximately constant fractionation of about –5‰ is achieved at 520°C. In this work, we present isotope ratio mass spectrometry (IRMS) δ13C results for 14C reference materials graphitized at 550°C with variable amounts of zinc. Based on the results obtained from the addition of 20, 35, and 50 mg of zinc, we conclude that a slightly lower variation in 13C isotope fractionation during graphitization is obtained with less zinc. Moreover, the average isotopic fractionation is not altered by increasing the graphitization temperature from 520°C to 550°C.

In this study, surface texturing and hydrogenated amorphous carbon (a-C:H) diamond-like carbon (DLC) coating was combined to evaluate the coating performance at various temperatures in oil lubricated reciprocating sliding tests. Micro dimples were created by laser surface texturing on M2 steel using a Pico second laser. DLC coating was deposited by hybrid magnetron sputtering on textured substrates. Textured a-C:H showed stable coefficient of friction at 30, 80, and 125 °C compared to un-textured a-C:H. At 30 °C, graphitization was not observed for both textured and un-textured DLC coating. Graphitization was more pronounced in the case of un-textured a-C:H at 80 and 125 °C. Results show that, at all temperatures tested (30–125 °C), DLC textured samples showed higher wear resistance compared to un-textured DLC coating. The improvement in wear resistance can be explained by the lower graphitization of textured DLC coating. Lower graphitization in the case of textured DLC might be due to the wear particle capturing and lubricant retention ability of textures.

This paper describes all the major procedures adopted by the Scottish Universities Environmental Research Centre (SUERC) Radiocarbon Dating Laboratory. This includes sample pretreatment, graphite production, accelerator mass spectrometry (AMS) measurement, associated stable isotope measurements, data handling, and age calculations, but with the main emphasis being on the chemical pretreatment methods. All of the above enable the laboratory to provide a complete analytical service comprising advice on sample selection, preparation and analysis of samples, and Bayesian analysis of resulting 14C (and other) data. This applies to both our research and commercial activities. The pretreatment methods that we mainly focus on are used to remove contaminant carbon from a range of sample types or to isolate a particular chemical fraction from a sample prior to combustion/hydrolysis, graphitization, and subsequent AMS 14C measurement. The methods described are for bone (collagen extraction, with and without ultrafiltration), cremated bone, tooth enamel, charcoal, grain, carbon residues, shell, wood (including alpha-cellulose isolation), peat, sediments, textiles, fuel/biofuel, and forensic samples.

Ti electrodes were directly deposited at different positions on diamond-like carbon (DLC) films to form horizontal and longitudinal electric fields on their surfaces. The ID/IG ratio increased with the sp3 content in the membrane when the DLC film was laser-irradiated and the electric field intensity was 0 V/cm. The bias electric field intensity increased from 0 to 1000 V/cm, and the corresponding laser-induced damage threshold (LIDT) increased. The three-dimensional damage morphology of the DLC film with two different electrode structures was observed when the electric field intensity was 220 V/cm. Two types of electrode structures were observed in the Raman spectra under an electric field intensity of 110 V/cm and laser energy densities of 0 and 1.56 J/cm2. Results showed that the horizontal bias field had a more obvious influence than the longitudinal electric field on the decrease of the sp3–sp2 hybridization, preventing the formation of sp2 clusters, thereby slowing down the graphitization process of DLC. Applying the bias field to the DLC film could slow down the DLC film graphitization process and improve the LIDT of the DLC film.

A new radiocarbon preparation facility was set up in 2010 at the Godwin Laboratory for Palaeoclimate Research, at the University of Cambridge. Samples are graphitized via hydrogen reduction on an iron powder catalyst before being sent to the Chrono Centre, Belfast, or the Australian National University for accelerator mass spectrometry (AMS) analysis. The experimental setup and procedure have recently been developed to investigate the potential for running small samples of foraminiferal carbonate. By analyzing background values of samples ranging from 0.04 to 0.6 mg C along with similar sized secondary standards, the setup and experimental procedures were optimized for small samples. “Background” modern 14C contamination has been minimized through careful selection of iron powder, and graphitization has been optimized through the use of “small volume” reactors, allowing samples containing as little as 0.08 mg C to be graphitized and accurately dated. Graphitization efficiency/fractionation is found not to be the main limitation on the analysis of samples smaller than 0.07 mg C, which rather depends primarily on AMS ion beam optics, suggesting further improvements in small sample analysis might yet be achieved with our methodology.

This article reports the microstructural characteristics of various petroleum and pitch based nuclear graphites (IG-110, NBG-18, and PCEA) that are of interest to the next generation nuclear plant program. Bright-field transmission electron microscopy imaging was used to identify and understand the different features constituting the microstructure of nuclear graphite such as the filler particles, microcracks, binder phase, rosette-shaped quinoline insoluble (QI) particles, chaotic structures, and turbostratic graphite phase. The dimensions of microcracks were found to vary from a few nanometers to tens of microns. Furthermore, the microcracks were found to be filled with amorphous carbon of unknown origin. The pitch coke based graphite (NBG-18) was found to contain higher concentration of binder phase constituting QI particles as well as chaotic structures. The turbostratic graphite, present in all of the grades, was identified through their elliptical diffraction patterns. The difference in the microstructure has been analyzed in view of their processing conditions.