Publications by authors named "Braden Sullivan"

14 Publications

  • Page 1 of 1

Photo-polymerization kinetics of a dental resin at a high temporal resolution.

J Mech Behav Biomed Mater 2021 Dec 7;124:104884. Epub 2021 Oct 7.

Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada. Electronic address:

Objectives: This study: 1) aims to measure with high temporal resolution the intrinsic rate of the degree of conversion (DC) of a dental resin-based composite (RBC) photo-cured at two irradiances; 2) aims to determine the transition time at which the DC rate is maximum; 3) used two different irradiances to measure the shift in transition time; 4) aims to compare transition times measured using DC and shrinkage strain.

Methods: Samples (n = 20) 1 mm thick by 10 mm diameter of Filtek One bulk-fill restorative A2 shade (3M Oral Care) were photocured for 20 s with a single emission peak (wavelength centered at 455 nm) light-emitting-diode-based light-curing unit at irradiance levels of 890 mW/cm and 209 mW/cm, and initial sample temperature of T = 23 °C. The DC was measured in real-time using Attenuated Total Reflection (ATR) FTIR spectroscopy with a sampling rate of 13 DC data points per second. The data were analyzed within a phenomenological autocatalytic model. In addition, the axial shrinkage strain was measured using 3 samples of the RBC with the same outer dimensions and under similar experimental conditions using the bonded disk method and an interferometric technique.

Results: For the 890 mW/cm and 209 mW/cm irradiance levels, the DC with time was found to agree with the model enabling the determination of transition times of 0.66 ± 0.05 s and 2.3 ± 0.2 s, and the DC at these times of 5.5 ± 0.2% and 6.4 ± 0.2%. The maximum linear strain rate at 0.76 ± 0.01 s and 1.98 ± 0.02 s for the 890 mW/cm and 209 mW/cm irradiance levels, respectively, are within two standard deviations of the corresponding transition times.

Significance: At an irradiance level much greater than 1000 mW/cm, the photo-polymerization kinetics of a dental RBC may be too fast to be measured accurately using ATR-FTIR spectroscopy. A viable alternative to monitor the kinetics is through the measurements of the axial shrinkage strain employing the bonded disk method and an interferometric technique.
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http://dx.doi.org/10.1016/j.jmbbm.2021.104884DOI Listing
December 2021

Effect of repeated heating and cooling cycles on the degree of conversion and microhardness of four resin composites.

J Esthet Restor Dent 2021 Aug 23. Epub 2021 Aug 23.

Department of Dental Clinical Sciences, Faculty of Dentistry, Dalhousie University, Halifax, Canada.

Objective: This study evaluated the effect of repeatedly heating and cooling four resin-based composites (RBCs) for up to six cycles.

Materials And Methods: Four commercial RBCs were heated to 68°C and cooled to room temperature for up to six cycles before photocuring at 30°C. Specimens spent a total of 0, 30, 60, 90, 120, 150 min, or 7 days at 68°C. The degree of conversion (DC) was measured at the bottom of the specimens immediately after photocuring. The Vickers microhardness was measured at the top and bottom of the RBC surfaces 24 h after photocuring. The data were analyzed using one-way analysis of variance, Dunnett's or Bonferroni post-hoc tests, and Spearman correlation analysis (α = 0.05).

Results: For two brands of RBC, the DC decreased at various time points; however, these decreases were small, and there was no correlation (negative or positive) between the number of heating cycles and the DC for any of the RBCs. Repeated heated and cooling resulted in small changes in the hardness (compared to the control) in both directions (Dunnett; p < 0.05). Two of the RBCs showed a significant, positive correlation between the number of heating cycles and their hardness at the bottom surface.

Conclusion: Repeated heating, cooling, and then reheating the RBCs for up to 1 week had little overall effect on their DC and microhardness values. The 2 mm thick specimens of all four RBCs achieved a bottom: top hardness ratio exceeding 0.8 after a 20 s exposure to light from a commercial LED curing light CLINICAL SIGNIFICANCE: Six repeated dry heating and cooling cycles of up to 1 week in duration had little effect on the DC and the microhardness of four commercial resin-based composites.
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http://dx.doi.org/10.1111/jerd.12815DOI Listing
August 2021

The light-curing unit: An essential piece of dental equipment.

Int Dent J 2020 Dec 21;70(6):407-417. Epub 2020 Jul 21.

Faculty of Dentistry, Dalhousie University, Halifax, NS, Canada.

Introduction: This article describes the features that should be considered when describing, purchasing and using a light-curing unit (LCU).

Methods: The International System of Units (S.I.) terms of radiant power or radiant flux (mW), spectral radiant power (mW/nm), radiant exitance or tip irradiance (mW/cm ), and the irradiance received at the surface (also in mW/cm ) are used to describe the output from LCU. The concept of using an irradiance beam profile to map the radiant exposure (J/cm ) from the LCU is introduced.

Results: Even small changes in the active tip diameter of the LCU will have a large effect on the radiant exitance. The emission spectra and the effects of distance on the irradiance delivered are not the same from all LCUs. The beam profile images show that using a single averaged irradiance value to describe the LCU can be very misleading. Some LCUs have 'hot spots' of high radiant exitance that far exceed the current ISO 10650 standard. Such inhomogeneity may cure the resin unevenly and may also be dangerous to soft tissues. Recommendations are made that will help the dentist when purchasing and then safely using the LCU.

Conclusions: Dental manufacturers should report the radiant power from their LCU, the spectral radiant power, information about the compatibility of the emission spectrum from the LCU with the photoinitiators used, the active optical tip diameter, the radiant exitance, the effect of distance from the tip on the irradiance delivered, and the irradiance beam profile from the LCU.
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http://dx.doi.org/10.1111/idj.12582DOI Listing
December 2020

Post-curing in dental resin-based composites.

Dent Mater 2018 09 23;34(9):1367-1377. Epub 2018 Jun 23.

Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada. Electronic address:

Objective: To determine the post-curing in six commercial contemporary resin-based composites (RBCs) using axial shrinkage, the degree of conversion, and Vickers hardness.

Methods: Five Bulk Fill and one conventional RBCs from three companies were selected with a wide range of filler volume content. The axial shrinkage of samples that were 1.00mm thick by 9-10mm diameter was measured using a modified bonded disk method over a time between 15h and 19h at temperatures of 26°C and 34°C (mouth temperature). The degree of conversion (DC) was collected continuously for 10min using mid-infrared spectroscopy in the attenuated total reflectance geometry. Vickers hardness was measured at 1h post-irradiation using a load of 300gf. For all three tests, the samples were irradiated at five exposure times, 20, 5, 3, 1.5 and 1s with a light curing unit radiant exitance of 1.1W/cm. Three samples (n=3) were used for each experimental condition.

Results: After light exposure, the axial shrinkage and degree of conversion exhibited a functional time dependence that was proportional to the logarithm of time. This suggests an out-of-equilibrium polymer composite glass that is transitioning to thermal equilibrium. At a sufficiently long time and among the RBCs investigated, the shrinkage related physical aging rate was found to vary between 1.34 and 2.00μm/log(t). The rate was a function of the filler content. Furthermore, 15h after light exposure, the post-curing shrinkage was estimated to be an additional 22.5% relative to the shrinkage at 100s for one RBC at T=34°C. The hardness in the photo-cured RBC was varied by using different light exposure times. The first two experimental techniques show that the higher the initial DC 10min after light exposure, the smaller is the post-curing shrinkage related and DC related physical aging rates. A direct correlation was observed between the shrinkage related and the DC related physical aging rates.

Significance: Post-curing shrinkage should be evaluated for longer than 1h. The post-curing shrinkage 15h after light exposure in dental RBCs can be appreciable. The long-term development of built-in stress within the tooth wall structure may shorten the restoration's lifespan.
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http://dx.doi.org/10.1016/j.dental.2018.06.021DOI Listing
September 2018

Erratum to: Effect of mold type, diameter, and uncured composite removal method on depth of cure.

Clin Oral Investig 2016 Nov;20(8):2321

Department of Dental Clinical Sciences, Faculty of Dentistry, Dalhousie University, Halifax, NS, Canada.

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http://dx.doi.org/10.1007/s00784-016-1733-3DOI Listing
November 2016

Effect of mold type, diameter, and uncured composite removal method on depth of cure.

Clin Oral Investig 2016 Sep 3;20(7):1699-707. Epub 2015 Dec 3.

Dalhousie University, Halifax, NS, Canada.

Objective: This study compared the effects of mold material and diameter on the thickness of cured composite remnants and depth of cure (DOC) of resin-based composites (RBC).

Material And Methods: One Polywave® curing light was used to photo-cure two shades of the same "bulk-fill" RBC in 4, 6, or 10-mm internal diameter metal or white Delrin® molds. For 60 specimens, the uncured RBC was manually scraped away as described in the ISO 4049 depth of cure test. The remaining 60 specimens were immersed in tetrahydrofuran for 48 hours in the dark. Maximum lengths of remaining hard RBC and their DOC values were compared using analysis of variance (ANOVA) and Tukey-Kramer post hoc multiple comparison tests (α = 0.05).

Results: Specimen thickness and DOC were always greater using the white Delrin® molds compared to metal molds (p < 0.001). Increase in mold diameter significantly increased specimen thickness and DOC when made in the metal molds and in the 6-mm diameter Delrin® molds (p < 0.01). Increasing the diameter of the Delrin® molds to 10-mm did not increase specimen thickness or DOC. Sectioning and staining of specimens revealed an internal, peripheral transition zone of porous RBC in the solvent-dissolved specimens only.

Conclusion: Mold material and internal diameter significantly influenced cured composite remnant thickness as well as depth of cure. The existence of an outer region of RBC that is hard, yet susceptible to solvent dissolution, requires further investigation.

Clinical Relevance: The depth of cure results obtained from a 4-mm diameter metal mold may not represent the true potential for evaluating composite depth of cure. A universally acceptable mold material and diameter size need to be established if this type of testing is to be useful for evaluating the relative performance of a given type of LCU and RBC.
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http://dx.doi.org/10.1007/s00784-015-1672-4DOI Listing
September 2016

Effect of a broad-spectrum LED curing light on the Knoop microhardness of four posterior resin based composites at 2, 4 and 6-mm depths.

J Dent 2016 Feb 22;45:14-8. Epub 2015 Nov 22.

Dental Clinical Sciences, Dalhousie University, P.O. Box 15000, Halifax, NS B3H4R2, Canada. Electronic address:

Objective: To measure the Knoop microhardness at the bottom of four posterior resin-based composites (RBCs): Tetric EvoCeram Bulk Fill (Ivoclar Vivadent), SureFil SDR flow (DENTSPLY), SonicFill (Kerr), and x-tra fil (Voco).

Methods: The RBCs were expressed into metal rings that were 2, 4, or 6-mm thick with a 4-mm internal diameter at 30°C. The uncured specimens were covered by a Mylar strip and a Bluephase 20i (Ivoclar Vivadent) polywave(®) LED light-curing unit was used in high power setting for 20s. The specimens were then removed and placed immediately on a Knoop microhardness-testing device and the microhardness was measured at 9 points across top and bottom surfaces of each specimen. Five specimens were made for each condition.

Results: As expected, for each RBC there was no significant difference in the microhardness values at the top of the 2, 4 and 6-mm thick specimens. SureFil SDR Flow was the softest resin, but was the only resin that had no significant difference between the KHN values at the bottom of the 2 and 4-mm (Mixed Model ANOVA p<0.05). Although the KHN of SureFil SDR Flow was only marginally significantly different between the 2 and 6-mm thickness, the bottom at 6-mm was only 59% of the hardness measured at the top.

Clinical Significance: This study highlights that clinicians need to consider how the depth of cure was evaluated when determining the depth of cure. SureFil SDR Flow was the softest material and, in accordance with manufacturer's instructions, this RBC should be overlaid with a conventional resin.
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http://dx.doi.org/10.1016/j.jdent.2015.11.004DOI Listing
February 2016

Examining exposure reciprocity in a resin based composite using high irradiance levels and real-time degree of conversion values.

Dent Mater 2015 May 21;31(5):583-93. Epub 2015 Mar 21.

Dalhousie University, Department of Dental Clinical Sciences, Faculty of Dentistry, Halifax, Canada. Electronic address:

Objective: Exposure reciprocity suggests that, as long as the same radiant exposure is delivered, different combinations of irradiance and exposure time will achieve the same degree of resin polymerization. This study examined the validity of exposure reciprocity using real time degree of conversion results from one commercial flowable dental resin. Additionally a new fitting function to describe the polymerization kinetics is proposed.

Methods: A Plasma Arc Light Curing Unit (LCU) was used to deliver 0.75, 1.2, 1.5, 3.7 or 7.5 W/cm(2) to 2mm thick samples of Tetric EvoFlow (Ivoclar Vivadent). The irradiances and radiant exposures received by the resin were determined using an integrating sphere connected to a fiber-optic spectrometer. The degree of conversion (DC) was recorded at a rate of 8.5 measurements a second at the bottom of the resin using attenuated total reflectance Fourier Transform mid-infrared spectroscopy (FT-MIR). Five specimens were exposed at each irradiance level. The DC reached after 170s and after 5, 10 and 15 J/cm(2) had been delivered was compared using analysis of variance and Fisher's PLSD post hoc multiple comparison tests (alpha=0.05).

Results: The same DC values were not reached after the same radiant exposures of 5, 10 and 15 J/cm(2) had been delivered at an irradiance of 3.7 and 7.5 W/cm(2). Thus exposure reciprocity was not supported for Tetric EvoFlow (p<0.05).

Significance: For Tetric EvoFlow, there was no significant difference in the DC when 5, 10 and 15J/cm(2) were delivered at irradiance levels of 0.75, 1.2 and 1.5 W/cm(2). The optimum combination of irradiance and exposure time for this commercial dental resin may be close to 1.5 W/cm(2) for 12s.
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http://dx.doi.org/10.1016/j.dental.2015.02.010DOI Listing
May 2015

Effect of the irradiance distribution from light curing units on the local micro-hardness of the surface of dental resins.

Dent Mater 2015 Feb 5;31(2):93-104. Epub 2014 Dec 5.

Bonn-Rhein-Sieg, University of Applied Sciences, Department of Natural Sciences, Rheinbach, Germany. Electronic address:

Objective: An inhomogeneous irradiance distribution from a light-curing unit (LCU) can locally cause inhomogeneous curing with locally inadequately cured and/or over-cured areas causing e.g. monomer elution or internal shrinkage stresses, and thus reduce the lifetime of dental resin based composite (RBC) restorations. The aim of the study is to determine both the irradiance distribution of two light curing units (LCUs) and its influence on the local mechanical properties of a RBC.

Methods: Specimens of Arabesk TOP OA2 were irradiated for 5, 20, and 80s using a Bluephase® 20i LCU in the Low mode (666mW/cm(2)), in the Turbo mode (2222mW/cm(2)) and a Celalux® 2 (1264mW/cm(2)). The degree of conversion (DC) was determined with an ATR-FTIR. The Knoop micro-hardness (average of five specimens) was measured on the specimen surface after 24h of dark and dry storage at room temperature.

Results: The irradiance distribution affected the hardness distribution across the surface of the specimens. The hardness distribution corresponded well to the inhomogeneous irradiance distributions of the LCU. The highest reaction rates occurred after approximately 2s light exposure. A DC of 40% was reached after 3.6 or 5.7s, depending on the LCU. The inhomogeneous hardness distribution was still evident after 80s of light exposure.

Significance: The irradiance distribution from a LCU is reflected in the hardness distribution across the surface. Irradiance level of the LCU and light exposure time do not affect the pattern of the hardness distribution--only the hardness level. In areas of low irradiation this may result in inadequate resin polymerization, poor physical properties, and hence premature failure of the restorations as they are usually much smaller than the investigated specimens. It has to be stressed that inhomogeneous does not necessarily mean poor if in all areas of the restoration enough light intensity is introduced to achieve a high degree of cure.
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http://dx.doi.org/10.1016/j.dental.2014.11.003DOI Listing
February 2015

Correlation between the beam profile from a curing light and the microhardness of four resins.

Dent Mater 2014 Dec;30(12):1345-57

Dental Clinical Sciences, Dalhousie University, Halifax, NS, Canada.

Objective: To demonstrate the effect of localized irradiance and spectral distribution inhomogeneities of one LED-based dental light-curing unit (LCU) on the corresponding microhardness values at the top, and bottom surfaces of four dental resin-based composites (RBCs), which contained either camphorquinone (CQ) alone or a combination of CQ and monoacylphosphine oxide (TPO) as photoinitiators.

Methods: Localized irradiance beam profiles from a polywave LED-based LCU were recorded five times using a laser beam analyzer, without and with either a 400 nm or 460 nm narrow bandpass filter placed in front of the camera lens. Five specimens of each of the four RBCs (two containing CQ/TPO and two containing CQ-only) were exposed for 5-, 10-, or 30-s with the light guide directly on the top surface of the RBC. After 24 h, Knoop microhardness values were measured at 45 locations across the top and bottom surfaces of each specimen. Microhardness readings for each RBC surface and exposure time were correlated with localized patterns of the LCU beam profile, measured using the 400 nm and 460 nm bandpass filters. Spearman rank correlation was used to avoid relying on an assumption of a bivariate normal distribution for the KHN and irradiance.

Results: The local irradiance and spectral emission values were not uniformly distributed across the light tip. There was a strong significant positive correlation with the irradiance beam profile values from the LCU taken through bandpass filters and the microhardness maps of the RBC surfaces exposed for 5 and 10 s. The strength of this correlation decreased with increasing exposure time for the RBCs containing CQ only, and increased for the RBCs containing both CQ and TPO.

Conclusions: Localized beam and spectral distributions across the tip end of the light guide strongly correlated with corresponding areas of microhardness in both the top and bottom surfaces among four RBCs with different photoinitiator contents. Significance: A light-curing unit with a highly inhomogeneous light output can adversely affect localized microhardness of resin-based composites and this may be a contributing factor for premature failure of a restoration.
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http://dx.doi.org/10.1016/j.dental.2014.10.001DOI Listing
December 2014

Localised irradiance distribution found in dental light curing units.

J Dent 2014 Feb 25;42(2):129-39. Epub 2013 Nov 25.

Dental Clinical Sciences, Dalhousie University, Halifax, NS, Canada.

Objective: To measure the localised irradiance and wavelength distributions from dental light curing units (LCUs) and establish a method to characterise their output.

Methods: Using a laboratory grade integrating sphere spectrometer system (Labsphere and Ocean Optics) the power, irradiance, and spectral emission were measured at the light tips of four LCUs: one plasma-arc (PAC) unit, one single peak blue light-emitting diode (blue-LED) unit, and two polywave LED (poly-LED) units. A beam profiler camera (Ophir Spiricon) was used to record the localised irradiance across the face of the light tips. The irradiance-calibrated beam profile images were then divided into 45 squares, each 1mm(2). Each square contained the irradiance information received from approximately 3200 pixels. The mean irradiance value within each square was calculated, and the distribution of irradiance values among these 45 squares across the tip-ends was examined. Additionally, the spectral emission was recorded at various regions across each light tip using the integrating sphere with a 4-mm diameter entrance aperture.

Results: The localised irradiance distribution was inhomogeneous in all four lights. The irradiance distribution was most uniformly distributed across the PAC tip. Both the irradiance and spectral emission from the poly-LED units were very unevenly distributed.

Conclusions: Reporting a single irradiance value or a single spectral range to describe the output from a curing light is both imprecise and inappropriate. Instead, an image of both the irradiance distribution and the distribution of the spectral emission across the light tip should be provided.

Clinical Significance: The localised beam irradiance profile at the tip of dental LCUs is not uniform. Poly-LED units may deliver spectrally inhomogeneous irradiance profiles. Depending on the photoinitiator used in the RBC and the orientation of the LCU over the tooth, this non-uniformity may cause inadequate and inhomogeneous resin polymerisation, leading to poor physical properties, and premature failure of the restoration.
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http://dx.doi.org/10.1016/j.jdent.2013.11.014DOI Listing
February 2014

Evaluation of the SO(2) and NH(3) gas adsorption properties of CuO/ZnO/Mn(3)O(4) and CuO/ZnO/NiO ternary impregnated activated carbon using combinatorial materials science methods.

ACS Comb Sci 2013 Feb 15;15(2):101-10. Epub 2013 Jan 15.

Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia, Canada B3H 3J5.

Impregnated activated carbons (IAC) are widely used materials for the removal of toxic gases in personal respiratory protection applications. The combinatorial method has been employed to prepare IACs containing different types of metal oxides in various proportions and evaluate their adsorption performance for low molecular weight gases, such as SO(2) and NH(3), under dry conditions. Among the metal oxides used for the study, Mn(3)O(4) was found to have the highest capacity for retaining SO(2) gas under dry conditions. NiO and ZnO were found to have similar NH(3) adsorption capacities which are higher than the NH(3) capacities observed for the other metal oxide impregnants used in the study. Although Cu- or Zn-based impregnants and their combinations have been extensively studied and used as gas adsorbents, neither Mn(3)O(4) nor NiO have been incorporated in the formulations used. In this study, ternary libraries of IACs with various combinations of CuO/ZnO/Mn(3)O(4) and CuO/ZnO/NiO were studied and evaluated for their adsorption of SO(2) and NH(3) gases. Combinations of CuO, ZnO, and Mn(3)O(4) were found to have the potential to be multigas adsorbents compared to formulations that contain NiO.
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http://dx.doi.org/10.1021/co3001132DOI Listing
February 2013

SO2 and NH3 gas adsorption on a ternary ZnO/CuO/CuCl2 impregnated activated carbon evaluated using combinatorial methods.

ACS Comb Sci 2012 Jan 13;14(1):31-7. Epub 2011 Dec 13.

Department of Physics, Dalhousie University, Halifax, Nova Scotia, Canada.

Ternary libraries of 64 ZnO/CuO/CuCl(2) impregnated activated carbon samples were prepared on untreated or HNO(3)-treated carbon and evaluated for their SO(2) and NH(3) gas adsorption properties gravimetrically using a combinatorial method. CuCl(2) is shown to be a viable substitute for HNO(3) and some compositions of ternary ZnO/CuO/CuCl(2) impregnated carbon samples prepared on untreated carbon provided comparable SO(2) and NH(3) gas removal capacities to the materials prepared on HNO(3)-treated carbon. Through combinatorial methods, it was determined that the use of HNO(3) in this multigas adsorbent formulation can be avoided.
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http://dx.doi.org/10.1021/co200127gDOI Listing
January 2012

Gas adsorption properties of the ternary ZnO/CuO/CuCl(2) impregnated activated carbon system for multigas respirator applications assessed through combinatorial methods and dynamic adsorption studies.

ACS Comb Sci 2011 Nov 13;13(6):639-45. Epub 2011 Oct 13.

Department of Physics, Dalhousie University , Halifax, Nova Scotia, Canada.

A ternary library of 64 ZnO/CuO/CuCl(2) impregnated activated carbon samples was synthesized and screened automatically using a combinatorial (combi) method. The ability of the samples to adsorb toxic gases was screened gravimetrically. The stoichiometric ratio of reaction (SRR) between the moles of toxicant and the total moles of impregnant was obtained from the calculated mass increase of the samples after chemisorption, with a high SRR indicating high efficiency of toxicant removal. The combi samples that exhibited good dry SO(2) and NH(3) adsorption were prepared in bulk using the incipient wetness method and were evaluated for multigas respirator function by dynamic adsorption studies of SO(2), NH(3), HCN, and C(6)H(12) gases in either dry or humid conditions at ambient temperature. The bulk samples showed equivalent gas adsorption capacities when exposed to the different challenge gases indicating the value of the combi method for initial screening. Cu(2)Cl(OH)(3) was identified to be a potential multigas adsorbent.
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http://dx.doi.org/10.1021/co200121cDOI Listing
November 2011
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