We present the results of laser ablations cleanness process on bronzes covered by a chloride patina in two different media: marine water and air. The bronze chloride disease was obtained treating commercial bronzes w...We present the results of laser ablations cleanness process on bronzes covered by a chloride patina in two different media: marine water and air. The bronze chloride disease was obtained treating commercial bronzes with HCI 37%, for 190 h. X-ray photoelectron spectroscopy and optical images taken on treated samples show the formation of a CuCIJCu2CI2 patina of about 300 m Laser ablation reduces in both medium the patina thickness at few microns without changing the chemical composition of bronze. X-ray analysis show the most effectiveness of ablation procedure in marine water where its only effect is the patina reduction without introducing changes in bronze chemical composition. Ablation in air, instead, reduces the patina but favors the adsorption of air oxygen and carbon on sample surfaces and a progressive "carbonization" of samples.展开更多
This work is a study of effect of laser ablation in different medium on silver artifacts. The effectiveness of laser ablation cleanness methods was evaluated in air, water and vacuum condition. The samples were subjec...This work is a study of effect of laser ablation in different medium on silver artifacts. The effectiveness of laser ablation cleanness methods was evaluated in air, water and vacuum condition. The samples were subjected to HC1 treatment for several hours to simulate the formation of chloride patina on marine archeological artifacts. Laser ablation removes the patina in all medium, reducing its thickness from 300 to few microns in air and water and eliminating completely the chlorine in vacuum conditions. However, it was observed the formation, during cleanness of a white patina in air and water and an increasing of oxygen amount on surface. This indicate that in ambient reach in oxygen laser ablation favorite the oxygen absorbance on surface and the formation of a thin layer of AgO which dulls the surface. This hypothesis is confirmed by the results of laser ablation in vacuum conditions where surface tarnishing was not observed. So, laser ablation in vacuum condition was indicated as the most effective procedure to clean silver artifacts.展开更多
Uneven distribution of minor metals and migration of isotopes in polymeric material (polypropylene) - originating under certain physical and chemical conditions-could possibly affect the stability and bio-compatibil...Uneven distribution of minor metals and migration of isotopes in polymeric material (polypropylene) - originating under certain physical and chemical conditions-could possibly affect the stability and bio-compatibility of such material. Unusually high levels of embedded surface metal isotopes from migration effects could affect studies such as tissue engineering and biospecific adhesion of cells to polymeric surfaces. There is, therefore, a general need to know the distribution of metal isotopes in such polymeric materials. We have developed an ultrasensitive technique for assessing the isotopic distribution in polymer matrices, and studying migration of metal isotopes. The technique uses laser ablation linked to an ICP-MS instrument. It is semi-quantitative and capable of high-resolution detection over a wide range of elemental levels. Polymers usually contain catalytic residues and other minor metal impurities. Some of the isotopes of these metals migrate to the surface, while others remain embedded deep in the polymeric product. Such unwanted metallic residues and isotopes could be a potential hazard, and ablative laser technology has the ability to study homogeneity of such distributions in the polymer matrix. The aim of this paper, therefore, is to explore the potential of our method for studying isotope migration using suitable polypropylene samples.展开更多
An in-situ microanalysis of Pb isotopic compositions in sulfide minerals is carried out by using femtosecond laser-ablation multi-collector inductively coupled plasma mass spectrometry (fsLA-MC-ICP-MS). High-tempera...An in-situ microanalysis of Pb isotopic compositions in sulfide minerals is carried out by using femtosecond laser-ablation multi-collector inductively coupled plasma mass spectrometry (fsLA-MC-ICP-MS). High-temperature-activated carbon was used to filter Hg contained in the carrier gas, which reduced the Hg background signal by 48% and also lowered the detection limit of the analysis. Fractionation and mass discrimination effects existing in the ICP-MS analytical processes were corrected using an internal reference T1 in conjunction with an external reference NIST SRM 610. The proposed method was used to an- alyze the Pb isotopic compositions of chalcopyrite, pyrite, and sphalerite from the Dulong Sn-Zn-In polymetallic ore district. The results showed that in this ore district, the sulfide minerals and different grains of the same sulfide mineral show a large variation in Pb content up to 1000-fold. The studied pyrites show relatively higher Pb contents and homogeneous Pb isotopic compositions, whereas the sphalerites have low Pb contents but most variable Pb isotopic compositions. It is suggested that the large variation of Pb isotopic composition may reflect a late hydrothermal superimposition on the primary sulfide formation. In addition, radiogenic Pb accumulated by radioactive decay of trace amounts of U over time in the host minerals may also be one of the causes for the large variation range of Pb content and Pb isotopic composition of those low-Pb sphalerites. Chalcopyrite and sphalerite grains with Pb content greater than 10 ppm presented a consistent Pb isotopic distribution, whereas all the sulfide grains with Pb content greater than 100 ppm had consistent Pb isotopic composition within 2s measurement uncertainties. The in-situ analysis of Pb isotopic composition agreed well with the results obtained by conventional chemical methods within 2s measurement uncertainties, indicating that the data obtained by fsLA-MC-ICP-MS are reliable. Additionally, this study indicates that the Pb isotopic composition could truthfully record the source of ore-forming minerals only for sulfide minerals with high Pb content. On the contrary, the Pb isotopic composition of low-Pb sulfide minerals may be affected by trace amounts of U in the host minerals that may lead to a highly radiogenic Pb isotope ratio. Alternatively, it is also possible that late fluid metasomatic overprinting may alter the Pb isotopic compositions.展开更多
文摘We present the results of laser ablations cleanness process on bronzes covered by a chloride patina in two different media: marine water and air. The bronze chloride disease was obtained treating commercial bronzes with HCI 37%, for 190 h. X-ray photoelectron spectroscopy and optical images taken on treated samples show the formation of a CuCIJCu2CI2 patina of about 300 m Laser ablation reduces in both medium the patina thickness at few microns without changing the chemical composition of bronze. X-ray analysis show the most effectiveness of ablation procedure in marine water where its only effect is the patina reduction without introducing changes in bronze chemical composition. Ablation in air, instead, reduces the patina but favors the adsorption of air oxygen and carbon on sample surfaces and a progressive "carbonization" of samples.
文摘This work is a study of effect of laser ablation in different medium on silver artifacts. The effectiveness of laser ablation cleanness methods was evaluated in air, water and vacuum condition. The samples were subjected to HC1 treatment for several hours to simulate the formation of chloride patina on marine archeological artifacts. Laser ablation removes the patina in all medium, reducing its thickness from 300 to few microns in air and water and eliminating completely the chlorine in vacuum conditions. However, it was observed the formation, during cleanness of a white patina in air and water and an increasing of oxygen amount on surface. This indicate that in ambient reach in oxygen laser ablation favorite the oxygen absorbance on surface and the formation of a thin layer of AgO which dulls the surface. This hypothesis is confirmed by the results of laser ablation in vacuum conditions where surface tarnishing was not observed. So, laser ablation in vacuum condition was indicated as the most effective procedure to clean silver artifacts.
文摘Uneven distribution of minor metals and migration of isotopes in polymeric material (polypropylene) - originating under certain physical and chemical conditions-could possibly affect the stability and bio-compatibility of such material. Unusually high levels of embedded surface metal isotopes from migration effects could affect studies such as tissue engineering and biospecific adhesion of cells to polymeric surfaces. There is, therefore, a general need to know the distribution of metal isotopes in such polymeric materials. We have developed an ultrasensitive technique for assessing the isotopic distribution in polymer matrices, and studying migration of metal isotopes. The technique uses laser ablation linked to an ICP-MS instrument. It is semi-quantitative and capable of high-resolution detection over a wide range of elemental levels. Polymers usually contain catalytic residues and other minor metal impurities. Some of the isotopes of these metals migrate to the surface, while others remain embedded deep in the polymeric product. Such unwanted metallic residues and isotopes could be a potential hazard, and ablative laser technology has the ability to study homogeneity of such distributions in the polymer matrix. The aim of this paper, therefore, is to explore the potential of our method for studying isotope migration using suitable polypropylene samples.
基金supported by the National Natural Science Foundation of China(Grant Nos.41427804,41421002,41373004)Program for Changjiang Scholars and Innovative Research Team in University(Grant No.IRT1281)the MOST Research Foundation from the State Key Laboratory of Continental Dynamics(Grant No.BJ08132-1)
文摘An in-situ microanalysis of Pb isotopic compositions in sulfide minerals is carried out by using femtosecond laser-ablation multi-collector inductively coupled plasma mass spectrometry (fsLA-MC-ICP-MS). High-temperature-activated carbon was used to filter Hg contained in the carrier gas, which reduced the Hg background signal by 48% and also lowered the detection limit of the analysis. Fractionation and mass discrimination effects existing in the ICP-MS analytical processes were corrected using an internal reference T1 in conjunction with an external reference NIST SRM 610. The proposed method was used to an- alyze the Pb isotopic compositions of chalcopyrite, pyrite, and sphalerite from the Dulong Sn-Zn-In polymetallic ore district. The results showed that in this ore district, the sulfide minerals and different grains of the same sulfide mineral show a large variation in Pb content up to 1000-fold. The studied pyrites show relatively higher Pb contents and homogeneous Pb isotopic compositions, whereas the sphalerites have low Pb contents but most variable Pb isotopic compositions. It is suggested that the large variation of Pb isotopic composition may reflect a late hydrothermal superimposition on the primary sulfide formation. In addition, radiogenic Pb accumulated by radioactive decay of trace amounts of U over time in the host minerals may also be one of the causes for the large variation range of Pb content and Pb isotopic composition of those low-Pb sphalerites. Chalcopyrite and sphalerite grains with Pb content greater than 10 ppm presented a consistent Pb isotopic distribution, whereas all the sulfide grains with Pb content greater than 100 ppm had consistent Pb isotopic composition within 2s measurement uncertainties. The in-situ analysis of Pb isotopic composition agreed well with the results obtained by conventional chemical methods within 2s measurement uncertainties, indicating that the data obtained by fsLA-MC-ICP-MS are reliable. Additionally, this study indicates that the Pb isotopic composition could truthfully record the source of ore-forming minerals only for sulfide minerals with high Pb content. On the contrary, the Pb isotopic composition of low-Pb sulfide minerals may be affected by trace amounts of U in the host minerals that may lead to a highly radiogenic Pb isotope ratio. Alternatively, it is also possible that late fluid metasomatic overprinting may alter the Pb isotopic compositions.