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    Zinc Getter Nps

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    Dr. Astha

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    © All Rights Reserved
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    of 21
    2) United States Patent Hunyadi Murph et al. (54) METHOD OF CAPTURING OR TRAPPIN ZINC USING ZINC GETTER MATERIALS oy + Nuclear Solu (US) Applicant: Savannah Ris LLC, Aiker (72) Inventors: Simona E. Hunyadi Murph, North Augusta, SC (US); Paul S. Korinko, Aken, SC (US) Savannah River Nuclear Solu LLC, Aiken, SC (US) (73) Assignee: (4) Notice: Subjoct to any disclaimer the term of this patent is extended or adjusted under 35 USC. 1846) by 0 days. 21) Appl. Now 157056,699 (22) Filed: Feb. 29, 2016 Gn Im. C1, BOID 53704 BOL 2002 (2005.01) (2006.01) (2006.01), ‘BOLD 53/04 (2013.01); BOLT 20/02 (2013 01); nozs 2028016 (2013.01; BoD 1253/1122 2013.01); BOID 2253304 (2013.01): BOLD 2257/60 (2013.01) (58) Fleld of Classiication Search oc BBOID $3404; BOND 2253/1122; BOLD 2283/30; BOLD 2257/60, BOL 20°02; BOL 20/28016 spc 95/133; 977/503 See application file for complete search history. 66) References Cited USS, PATENT DOCUMENTS. som B B 102012 Asia-Far 92013, Chntonos AC Cote 'US009700829B1 US 9,700,829 BI Jul. 11, 2017 (10) Patent No.: (4s) Date of Patent: 900420 m2 eerarghavan al Rose Bo Roby eal 02-401 20110204660 AL 122011 Koo al 2120045582 AL* 22012 Gay exe 1006 227250 2O1AOITSSM AL* 62014 Porsherom o.oo. BOL 200266, 189 (OTHER PUBLICATIONS SRNL-STL-2011.0057, Elet of Pore Size on Trapping Zinc Vapors, Pal Koriko, Doe. 17, 2010 SRNL-STI-2011-00349, Preliminary Study of Methods to Chen cally Bind Zine, Paul Korinko, Jun 10,2011 SSRNL-ST12011-00472, Summary Report for Zine 65 Contains tion Conta, Pal Korn (4, 2011 SRNL-STI-2015-00625, Effect of Thermal Processes on Copper Tin Allo for Zine Getering, Gols. a, Oct 8.2013 SRNLSTI-2014.00078, Development and” Characeriation of ‘Nanomaterials for Zine Vapor Capture, Kovako, etal, TMS 2018 144" Aaa Mesting & Exitition, Mas 15-19, 3015, Osando, FL Sensitive Detection of 1,8 Using Gold Nanopstiles Decorated SWNT, Mabe et a, Analytical Chemistry, Jan 1 2010, 82(1} (Continved) Primary Examiner (74) Attorney Prank Lawrence Agent, or Firm —Dority & ning, PA. on ABSTRACT A method of tripping or capturing zine is disclosed. In particular, the method comprises a step of contacting a zine ‘vapor with a zine getter material. The zine getter material comprises nanoparticles and a metal substrate 23 Claims, 11 Drawing Sheets US 9,700,829 BL Page 2 66) References Cited (OTHER PUBLICATIONS Eft of Thermal Processes on Copper-Tia Alloys for Zine Geter: ing, Kornko, eal, Now. 1 2013, ‘Now Systoms for Waste Processing of Tritum-Contaning Gassesat the Savannah River Site, Poore, etal, Fusion Seience and Teck- nology 48.1 298301, Ja. 15.2008, Chemical Reviews 2012, Gold Nanoparticles in Chemical and Biological Sensing, Saha, etal, Fe. 2, 2012, 1128) pp. 2799 2m, * cited by examiner U.S. Patent Sul. 11, 2017 Sheet 1 of 11 US 9,700,829 B1 Figure 1 U.S. Patent Sul. 11, 2017 Sheet 2 of 11 US 9,700,829 B1 Copper S80655 Bronze Control (without nanoparticles) Before Zine Exposure (with gold nanoparticles) After Zine Exposure (with gold nanoparticles Figure 2 U.S. Patent Sul. 11, 2017 Sheet 3 of 11 US 9,700,829 B1 Figure3 U.S. Patent Jul. 11, 2017 Sheet 4 of 11 US 9,700,829 BL Au-Co Core-Shell Nanoparticles on ssw ‘Au Nanoparticles on SSW Figure 4 U.S. Patent Sul. 11, 2017 Sheet 5 of 11 US 9,700,829 B1 SSW Control (w/o nanoparticles) Au-Co Core-Shell Nanoparticles ‘on SSC Au Nanoparticles, ‘on SSC Au-Co Core-Shell ‘on BC Figure S U.S. Patent Sul. 11, 2017 Sheet 6 of 11 US 9,700,829 B1 Au-Co Core-Shell ‘Nanoparticles on CC (rst side) Au-Co Core-Shell Nanoparticles once (second side) Co Nanoparticles on CC Figure 6 U.S. Patent Sul. 11, 2017 Sheet 7 of 11 US 9,700,829 B1 E Figure? : > B® Bir oe at Aleta 7 Figures U.S. Patent Sul. 11, 2017 Sheet 8 of 11 US 9,700,829 B1 Au Nanoparticles on SSW oi fy os | | 0.2 | 1 2 { { 3 | | @au Boos | | | | | | Zn 0.02 | | 10 30 Sonication time (min) Figure 9a U.S. Patent Sul. 11, 2017 Sheet 9 of 11 US 9,700,829 B1 Au Nanoparticles on SSW (after Zn exposure) Mz. Sonicaton ie (in) Figure 9 U.S. Patent Jul. 11,2017 Sheet 10 of 11 US 9,700,829 B1 ‘Au-Co Core-Shell Nanoparticles on SSW (aller Za exposure) ° - Tl Sonication ime (min) Figure 9¢ U.S. Patent Jul. 11, 2017 Sheet 11 of 11 US 9,700,829 B1 ‘Au Nanoparticles on SSW Au Nanoparticles on SSW ‘Au Nanoparticles on SSW" (after Zn exposure and {after Zn exposure and ier Za exposure) sonicated for 30 minutes) —_sonicated for 60 minutes) Figue 10 Intensity (coun Diffraction Angle, 20(°) Figure 1) US 9,700,829 BI 1 METHOD OF CAPTURING OR TRAPPING ZINC USING ZINC GETTER MATERIALS FEDERAL RESEARCH STATEMENT. ‘This invention was made with Government support wader Contract No. DE-AC09-085R22470, awarded by the US. Department of Energy. The Government has certain rights i the invention BACKGROUND OF THE INVENTION “The ability 10 effectively and eficiently capture zine vapors is of importance, For instanee, radioactive zine can be detecied from extracted ritium-praducing bumble absorber rods that have been iradiated. Thus, in order 10 prevent radioactive contamination, it i desired to capture and trap the zine ‘Various physical and chemical methods of tapping and retaining, zine vapors have boen employed. However, in ‘certain instances, these methods employ materials whieh may not be suitable for use thigh temperatures. In pariew- ee materials. may not exhibit the necessary themmal stability when employed at high temperatures. As a result they may’ not be as elfeetive for tapping zine vapors. "Asa res there isa need to provide an eflcient method ‘of trapping Zine vapors. In particular, there is @ need (0 provide an eficent method by employing zine getter mate- Fials that are suitable for use at high temperatures SUMMARY OF THE INVENTION Aspects and advantages ofthe invention will be set Forth jin part inthe following description, o may be apparent from the description, or may be learned through practice of the In accordance with one embodiment ofthe present iaven= tion, a method of capturing or trapping Zine is disclosed. In Particular, the method comprises a step of contacting a zine vapor with a zine getter material. The zine getter material ‘comprises nanoparicles and # metal substrate. ‘These and other features, aspects and advantages of the present invention will hesome better understood with refer ‘ence tothe following description and appended claims. The fsocompanying drewings, which are incorporated in and ‘constitute a part of this specification, illustrate embodiments ‘of the invention and, together with the description, serve to ‘explain the priniples ofthe invention, BRIBE DESCRIPTION OF THE DRAWINGS Aull and enabling disclosure of the present invention, including the best mode thereof, directed o one of ordinary shill in the art is st forth inthe specification, which males reference to the appended figures, in which IG. 1 provides images of nanoparticle treated stainless steel woo! and untreated bronze pellets before and after zine vapor exposure; TIG, 2 provides images of copper, stainless steel, and bronze coupons before nanoparticle treatment and nanopar- ticle weated coupons before and aller zine exposure; and IG. 3 provides an FDX mapping analysis of gold nano- particles deposited onto stainless stect wool after ine vapor ‘exposure and SPM images ofthe zine deposits tapped by the gold nanoparticles; FIG. 4 provides SEM images before and after zine vapor ‘exposure of nanoparticles deposited on stainless steel wool: 0 o 2 FIG. § provides SEM images before and after zine vapor exposure of a stainless steel woo! control and substrates containing gokl-based andor cobalt-based nanoparticles FIG. 6 provides SEM images before and after zine vapor exposure of substrates containing gokl-based and/or cobalt based nanoparticles, FIG. 7 provides an analysis of the particle size of the ‘nanoparticles before and after zine vapor exposure: PIG. 8 provides data from an EDX analysis indicating the ‘ine content on the materials PIGS, 9a-9¢ provide data obtain from an ICP-MS analy FIG. 10 provides SEM images showing the effet of sonication aller zine exposure on a stainless steel wool sample containing gold nanoparticles; and FIG. 11 provides XRD data on a material containing gold nanoparticles and stainless steel coupons aller zine vapor exposure DETAILED DESCRIPTION OF THE INVENTION Reference now will he made in detail to embodiments of the invention, one or more examples of which are illustrated in the drawings. Fach example is provided by way of explanation ofthe invention, not litation ofthe inveation In fact, it will be apparent to those skilled in the art that various modifications and. variations ean be made in the present invention without departing from the scope or spirit ff the invention. For instance, features illuseated or scribed a8 part of one embodiment can be used with ‘nother embodiment to yield a still further embodiment. ‘Thus, iti intended thatthe present invention covers sch noifications and variations as come within the seape ofthe appended claims aod thei equivalents Tn general the present invention is directed to a method of eapturing or trapping zine, such as zine vapor. In pa sical, the method comprises a step of contacting Zine vapor with a zine getter material. For instance, the zine getter ‘material can comprise @ nanoparticle and a metal substrate ‘The present inventors have discovered thatthe method and ine getter materials disclosed herein ate elfetive for tap Ping zinc vapor As mentioned herein, the present invention is directed 10 cupping o capturing zine, sul as zine vapor The zinc may bean isotope of zine. For instance, in one embodiment, the ine may bea radioisotope of vine. in one particular embod ‘ment, the zine may be zine-65. In one embodiment, the zine may be attributed to or produced from a high vacuum thermal deposition process and/or apparatus ‘As mentioned herein, the present invention employs a vine getter material conisining @ nanoparticle and 2 metal substrate for pping or capturing the zine, The present inventors have discovered that these materials are effective Tor sich purpose. In particular, the present inventors have found thatthe nanoparticles ean exhibit unique properties due to their large strface area and quantum size elles “According tothe present invention, the zine getter mate ial contains a metal subsiate, The metal substrate may ‘include any metal known in the art. The metal substrate may comprise at lest one metal. For instanee, in one embod ‘ment, the metal substrate may comprise atleast two metals For instance, the metal substrate may be an alloy. In one embodiment, the motal substrate may include copper, tn, chromium, or a combination thereof. In one embodiment the metal substrate may include copper. In one particular embodiment, the metal substrate may include copper and tn US 9,700,829 BI 3 nbodiment, the metal substrate may include bronze. In another embodiment, the mictal substrate may include chromium. For instance, the metal substrate may inchide stainless steel. In addition, it should be understood thatthe metal substrate may consist essentially of or consist of the aforementioned metals, In general, the metal substrate may be provided having any configuration known in the ar. In general, the metal ‘substrate should he one that allo’s forthe adhesioa, depo- sition, andor nucleation of the nanoparticles disclosed herein. For instance, the metal substrate aay be inthe form ‘of a coupon, wool, a sereen, a rod, et. For instance, the metal subsirate may inelude, but isnot limited to, a eopper ‘coupon, a bronze coupon, a stainless steel coupon, stainless Steel wool, ec Tn one embodiment, the metal substrate includes more than 50 wt. % meta, such a8 75 wt. % oF more, such as 90 ‘wt % or more, such as 95 wt. % or more, such as 99 wt. % ‘or more, such as 99.9 wt. % oF more, such as 99.99 wt. % ‘or more, In one embodiment, the metal substrate consis ‘essentially of oF consists of metal. According to the present invention, the zinc getter mate- Fial contains a nanoparticle. According ta the present inven- tion, the sanopsiticle includes a metal. In genera it shoold be understood that any metal eapable of being provided as ‘a nanoparticle and performing as azine getter material may be employed according to the present disclosure. For instance, the nanoparticle may comprise gold, cobalt, of & ‘combination theres For instance, in one embodiment, the nanoparticle may comprise gold. Tn another embodiment, the nanoparticle may comprise enbslt. In a futher embodi- ‘ment, the nanoparticle may comprise both gold and cobalt. For instance, im one embodiment, the nanoparticle may comprise a gold/cobalt alloy. In addition, it should be understood tat the nanoparticles may consist essentially of ‘or consist of the aforementioned! metas In addition, the nanoparticle may be inthe form of any’ shape or configuration known in the art. For instance, the nanoparticles may’ be made of two different metals and may have a core-shell configuration. The weight ratio ofthe core to the shell can be 1 or more, sch as 10:1 of more, sich 8 25:1 or more, such as 40:1 oF more, suchas 50:1 ar more and 250:1 or less, such as 150:1 or less, such as 100:1 or less, suchas 90:1 of les, such as 80:1 or less, such as 75: or less. Tn one embodiment, the weight ratio may be from 50:1 to 75s In one embodiment, the nanoparticle may comprise both old and cobalt in core-shell configuration. For instance, the core may include gold while the shell may inelude cobalt ‘or alternatively the core may inelode cobalt while the shell, may include gold. In one embodiment, the weight ratio of the care, whether gold or cobalt, othe shell, comprising the ‘ther of gold or cobalt, can be I:1 or more, such as 10:1 oF more, such as 25:1 or more, such as 40:1 or more, such as 50e1 or more and 280:1 oles, such as 150-1 of less, such a5 10021 or less, such as 90:1 or loss, such as 80:1 oF less, such a8 75:1 of less, Ia one embodiment, the weight ratio may be from 0:1 to 75:1. In one embodiment, the core includes gold while the shell includes eobalt having the aforementioned weight ratios. In another embodiment, the core may include a gold! ‘cobalt alloy while the sheli may be made of either gold or ‘cobalt or sitematively the core may be made of ether gold ‘or cobalt while the shell may be a gold/eobakt alloy. In one ‘embosdiment, the weight ratio of the gold to the cobalt in the alloy can be from 10:1 or less, such as 5:1 oles, such as 2.5: or les, such as 15:1 of les, steh 1:25 o¢ less to 1:10 0 o 4 ‘or more, sich a8 1:5 oF more, such as 1:3 oF more, such as 1:2. or more, such as 23 or more, such as 3:4 oF more, such as 4:5 or more, In one embodiment, the weight ratio of the {gold tothe cobalt inthe alloy is about I: In addition, the Aforemeationed core 1 shell weight ratios may apply. "The nanoparticles can he prechived wfilizing any method saenerlly knowa in the af. Such methods include, but are ‘ot limited to, wet chemistry approaches, reduction meth- ‘ds, nanolthography, physical vapor deposition, electro~ chemical approaches, sputtering, ec. For instance, in one embodiment, the nanoparticles ean be produced using. @ ‘eduction method. For instance, aqueous toluions contain: ‘ng the desired metal ean be boiled and reduced (e.g, citeate reduction) to obtzin the desired nanoparticles. ‘As mentioned herein, the zine getter material includes 3 nanoparticle ad a meal subsrate, In one embodiment, the ‘nanoparticles are present on the surface of the metal sub- strate, Without intending to be limited by theory, the nano- particles can providean increased surface area fr capturing fr tmpping the Zin, ‘The nanoparticles can be deposited, adhered, grown, et. ‘onto the metal substrate. Any method may be employed s0 Jong as the nanoparticles are capable of hing provided and retained by the metal substrate. For instance, various meth- fds such as electradeposition, vapor deposition, precipita- ‘ion, et. can be employed for providing nanoparticles on the ‘metal substrate ‘In one embodiment, the nanoparticles ean frst be synthe sized and therealter deposited or adhered onto the metal substrate, In this regard, they ean be deposited or adhered ‘nto the metal substrate wsing any method known inthe ar. Ta another “embodiment, nucleation and growth approach may be utilized. For instance, the nanoparticles an be grown onto the surface ofthe metal substrate. In this ‘regard, the nanoparticles ean be grown onto the substrates using uy method generally known in the aet. Without intending to be limited by theory, nuclestion and growth includes stp of ereating mele wherein such nucle’ serve fas templates for growth, Inone embodiment, the nanoparticles can be grown on the etal substrate using an aqueous soltion and employing conditions for producing the desired deposit size and shape ‘nto the metal substrate. For instance, the nanoparticles ean be synthesized in the presence of the metal substrate so that the nanopurtieles are grown onto the subsirat, For instance, the nanoparticles can grow and/or attach onto the substate via nucleation and growth of the erystal on the substrate ‘In general, the nanoparticles canbe in the form of diserete particles or aggregates on the meal substrate, Thus, before exposure 10 zine vapor, the nanoparticles may have an average particle size of § nm or greater, such a5 10 nm or ‘reat, such as 1 nm or greater, such as 20 nm or greater ‘and 800 nm or les, such as 600 mo less, such as $00 naa fof les, such as 400 nm or Fes, sich as 300 nm or fess, sich 1s 200 am or les, such as 150 nm or less, sue a 100 nm for les, stich as 50 nm oF less, The average particle size can be determined by analyzing the particle sizes from a micro raph obtained using a microscopy technique, soch as via Scanning electron microscopy. ‘In one embodiment, before zine exposure, the nanopar ticles on the metal subsiate may have a mulmodal (ez. ‘bimodal, trimodal, ete.) size distribution For instance, a first size distibution, such as nanoparticles in the form of ise crete particles may have an average particle sizeof 2 nm ar greater, such a $ nm or greater, such 2s 10 nm or greater, sch as 15 nm or grestr, such as 20 nm or grater and 50 ‘am of les, such a8 45 am of less, sue as 40 mor les, seh US 9,700,829 BI 5 ‘38.35 nm or les, such as 30 nm or less, Meanwhile, second distribution, suchas nanoparticles inthe form of aggregates, may have an average size of greater than 50 am, such as $3 1m or greater, such as 60 nm or greater, such as 65 nm oF rear, such a8 70 nm or greater, sued 2s 75 nm or greater fnd 150 am or les, stich as 130 nm or less, such as 128 am ‘oF less such as 100 nm oF less, such a8 90 amor less, such, fs 85 am or less. In one embodiment, a third distiation may also be present having an average size of preater than 150 nm, such as 175 nm or more, such as 200 nm ar more 1o 500-nm of les, such as 400 am oF less such as 300 am ‘or les, sueh as 250.nm or less. Any method known inthe ar, ‘or determining whether the particles havea multimodal size isiiburion can be employed, ‘By depositing, ahering, or growing the nanoparticles on the metal substrate, the nanoparticles may occupy the sur- face area ofthe metal substrate. In genera, the nanoparticles ‘occupy 5% oF more, such as 10% oF more, such as 15% oF more, such as 20% or more, such as 25% or more, such as 30R% or more, Such as 40% more, such as $0% or more and 5% or less, such as 80% or les, such as 70% or less, such 8 60% oF Tes, such as 50% oF less, seh a8 40% oF ess, suchas 30% oF less ofthe surface area ofthe metal substrate In one embodiment, the nanoparticles occupy only such pereentages of one side or surface of a metal substrate. “According to the method disclosed here, the 2ine getter materials, in particular the nanoparticles, are capable of trapping or capturing the zine, such as the zine vapors. For instance, the zine getter materials can he exposed t0 oF ‘contacted with zine Vapor for capturing or taping the same, ‘Without intending to be limited by theory, its believed thatthe zine alloys withthe metal(s) of the ssnoparicle and thus the nanoparticle is able to capture or trap the zinc. Without intending tobe limited by theory, itis believed that the zinc forms & metallic bond with the metal(s) of the nanoparticle, Such alloying caa form an intermetallic com- pound that can be confirmed by high resolution transmission ‘electron microscopy (HRTEM) andior X-ray diffraction (XRD). Without intending to be limited by theory, such alloying may provide aditional stability and ireversibility ‘ofthe materials upon expostire to zine vapor. Inston, the ‘ine may also be eapable of depositing or adhering onto the ictal substrate, In one embodiment, the zine geter materials presently disclosed may be able 'o tap the zine vapor in a chemical orm while avoiding the formation of a hydride. In one ‘embodiment, the zine peter materials disclosed herein may be capable of trapping or capturing zine without also acting as hydrogen getters. In addition, the method and materials, presently disclosed may also be employed and prevent or reduce the formation of various gases such as CH, NH, HS, ete. "The method presented herein may be conducted at any temperature in which zine vapors ean be present and are ‘capable of being captured/trapped or deposited onto the zine ‘geter materials. In one embodiment, the method may be ‘conducted at a temperature of from about 150° C. to about 500 C.,soch as fram about 250° C. to about 450° C., such 8 om about 300° C. to about 400° C., sth as fom about 325° C. 10 about 375° C. “The present inventors have discovered that the method and ine getter materials disclosed herein are effective for ‘eaphuring. and trapping. zine vapors. For instance, upon ‘exposure to zine vapor, the nanoparticles may inerease in, size, Thus, aller exposure to zine vapor, the nanoparticles may have an averige particle size of 5 nm or greater, sch ‘810 am or greater, such as 15 nm or greater, sel as 20 am 0 o 6 fo preter and 800 nm or less, sue as 600 nm or less, sue ‘as 500 am of les, such as 400 nm of less, such as 308 nz fr les, sueh as 200 am or les, such as 150 nm or less, such ‘a 100 um or les, such as $0 nm of less, The average particle Size ean be determined by analyzing the parle sizes Irom ‘a micrograph obtained using a microscopy technique, sich as via seanning electon microscopy. In addition, after zine exposure, the nanoparticles on the ‘metal substrate may also have a multimodal (c.., bimodal, ‘eimodal, ete) size distribution. For instance, the first dis ‘eibutioa referenced here, suchas nanoparticles in the form of diserete particles may experience an increase in the average particle size of about 5% or more, such as 10% or mon, such as 15% or more, such as 25% or more, such as 30% or more, such as 40% or more and 300% oF less, sch 8 200% oF les, such as 100% or les, such 28 90% oF les, such as 80% of less, such as 70% or less, such 2 6% oF less, sch as $096 oF les, suc as 40% or less, Such articles of the first distibution may have an average particle size of 2 nm or greater, suel as Sm or ureter, such as 10 nm or ‘greater, such as 15 nm or greater, such as 20 am or greater, Such as 30 nm or greater and 75 nm or less, such a5 6S nm fr less, such as $0/nm or les, such as 45 am or less, sch 40 nm or less, such a 38 nm or less, such as 30nm or less, sich a8 25 nm oF less, ‘Meanwhile, the socond distribution referenced herwin, seh as tanoparteles inthe form of sggrepates, may expe. rience an increase in the average particle size of about 1% ‘oF more, sch a8 5% oF mor, sich as 10% oF more, such as 15% of more, such as 25% or more, such a8 30% oF mone stich as 4% or more and 30K oF lest, sich as 200% or less, such as 100% or less, such as 90% or less, such a8 80% oF Tess, such as 70% oF less, such as 60% or est, such a8 50% of less, such as 40% or less. Such particles of the second istribution may have an average size of greater than 50 um, such as $5 nm or greater, such as 60 nm or greater, such as 65 nm or greater, sich as 70 nm of greater such a8 75 nm for greater and 175 of less, such as 150 nim of les, stich a= 130 nm or less, sich as 125 nm or less, stich a8 100 nm or Jess, sich as 9 am of fess, such a8 88 am oF less ‘In one embodiment, @ third distribution may also be present having an average size of greater that 150 am, such 8175 nm or mor, such a8 200 nm oe more, such 2s 300 nz for more 10 $00 nm or less, such as 400 nm or les, such as '300 nm or les, sich as 250 nm of less. Any method known in the art for determining whether the particles have a ‘multimodal size distribution can be employed. Tn one embodiment, when viewed under SEM or TEM, at least some of the zine may be present having a cubic (or isometric) mompbology Inaction, alter capturing or trapping zine, st least some of the nanoparticles containing the zine may have sizes of 200 nm or more, such as 280 nm oF more, such 300 nm or ‘mor, sich a8 350 nm oF more, and 800 nm oF less, sch as 700 nm or less, such as 600 mm or Tess, such as $00 nm or less, sch a8 400 nm or less ‘in this regatd, the weight ofthe zine getter materials can also be increased alter exposure to zine, For instance, the ‘weight ofthe zine getter materials ean inorease by 0.01 wt ‘OF more, such as 0.1 WT, % oF more, such as 0.2 Wt % oF mor, such as 0.5 wi. % oF more, such as 1 wt. % oF more, sch as 5 Wi. % oF moro, such as 10 Wt. % or more to 200 ‘et % or less, such as 100 wt % oF less, such as $0 wt % for less, sch as 25 wT. % or les, sch as 18 wt. % oF less, stich as 10 wt. 9 of les, such as S wt, % or less, such as 2 WL Soles, such a 15 Wt. % or les, such as 1 wi. % oF US 9,700,829 BI 7 less, In one embodiment, the zine can be present ‘amount sel that it saturates the nanoparticles Tn general, based on the amount of gold inthe nanopar- ticle, the weight ratio of zine to tht of the gold may be from 0.01 or more such as 0.1 or more, such as 0.2 or more, such, (03 or more, such as 0.4or more, such as 0S or more, such 880.6 ormore, suchas 0.7 or more, suchas 038 or more, such as Lor more to $0 or less, such as 25 or less, such as 10 oF Jess, such a8 5 of less, such as 4 of Tes, sch as 3 oF less, suchas 2.5 or les, such as 2 oF les, sth as 1.5 oF Hess, seh as Lor less, In general, based on the amount of cobalt in the nano- particle, the weight ratio of zinc to tat of the cobalt may be Tom 0.5 oF more, such as 1 or more, such as Sor more, such 8 1OoF more, such a8 1S of more, such as 20. more, sich 88 25 0r more, such a8 300 more, such as 40 F more, such as 45 oF more 10 100 or less, such as 90 or less, such as 80 ‘oF less sch as 70 oF less, sch as 60 a less, sich as 50 oF less, teh a 40 of es, sch as 30 F les, such a8 20 oF less. In one embodiment, the zine may be released from the ne getter materials. For instance, the Zine may be removed fom the materials by exposing the materials to sonication. Sonication may also be used to evaluate the zine retention tnd the adhesion ofthe zine to the materials. Other dezin- ‘ification methods include vacuum extraction at high tem- peratures and low pressures, comosion, ete. When present in Solution, the solution and ine can thereafter be furrhee processed as deste and necessary. I should be understood that other methods may also be employed for removing the “The method and materials disclosed herein ean have & umber of applications. For instance, the method can be tused to trap Zine, such as zine-65, that is detected from ‘erated tetium-producing, burnable absorber rods (IP- ARs). For instance, the method may be conducted during ‘8 vaeum processing step In this instance, the zine-65 may be an activation product of natural zinc. In general, the ine-65 extracted may produce a signature greater than the background "The present inventors have diseovered that when the nanoparticles are deposited nto the metal substrate, the zine _geiter materials can effectively and efficiently capture zine. Without intending toe limited by theory it is belived that the nanoparticles can be bound tothe substrate and handled salely such that the metal substrate serves as an eficient ‘setive anchoring site so that the nanoparticles can be ‘exposed to the zine vapors. This can allow for an easier ‘deployment and can be Used to resin the Zine vapor andor ‘gamma emitting materials inthe high radiations ares safely. As a result, this may also reduce personnel exposure, prevent product contamination, and reduce disposal cost, EXAMPLES Example 1Symthesis of Materials ‘Materials of various size, shape, morphologies and com- Positions were grown onto diferent substrate materials, Including copper coupon (CC), bronze coupon (BC), sane Jess steel coupons (SSC) and stainless stl wool (SSW). Nanoparticles of interest, including Av, Co, Au-Co eone- shell (CS), Aw—-Coalloy (A), and Au—Co--Co alloy-core- shell (ACC), were grown from aqueous solutions using ‘conditions that would produce the desired deposit size and shape. 0 o 8 Gold and cobalt nanoparticles Were prepared by a citrate seduction approach in the presence of supports, SSW, CC, SSC and BC. Gold nanoparticles were synthesized by heating an aque us solution having 1.25x10~*M Au" to boiling and adding 1 wt. % reducing agent (sodium citrate) solution, The boiling was continved vail the solution turned ruby eed, indicating the formation of gold nanoparticles ‘Cobalt nanoparticles were syuthesized by heating aa aqueous solution having 1-25x10~* M Co to boiling and adding a 1 wt. % reducing agent (Sodium citrate) solution ‘The boiling was continued tatil the solution tured light yellow, indicating the formation of eobalt nanoparticles ‘Goldcobalt alloy nanoparticles were prepared by asim Jar procedure by reducing a mixture of 1.25x10~M Av’ and 1.25.10 M Co", with a color change to light blue indicating the deposition of the alloy particles, ‘Core-shell Au-Co nanoparticles were prepared in 960 steps: (a) synthesis of Au (0) nanosphere core seeds and (b) Co-shell. Gold nanoparticles were synthesized by heating an aqueaus solution having 12510 M Au to boiling and ‘adding a 1 wt. % reducing agent (sodium citrate) solation “The boing was coatinved unt the solution turned ruby ee, indicating the formation of gold nanoparticles, The Co shell was added to these Au “seed” particles by adding 1.25%10~ ‘M Co” to boiling and adding a 1 wt. % reducing agent (Godtium citrate) solution, Au—Co—Co alloy-core-shell nanoparticles were pre- pared in two steps: (a) preparation of the Av—Co alloy nanosphenes and (b) preparation ofthe Au—Co alloy coated ‘with Co. Goidieobalt allay nanopaicles were prepared by 4 similar pocedare by reducing mixture of 1.25x10"M ‘Aut and 125410-* M Co, with a color change to light blue indicating the deposition ofthe alloy particles. The as prepared Au—Co alloy nanospheres prepared were used as Ssgods" for addition of a Co shell To this “seed” solution, 1.2510" MCo** was added to boiling followed by adding a1 wt. % reducing agent (sodium citrate) solution ‘he resulting nanoparticles were purified by three to five washings in deionized water Example 2—Zine Capturing Trapping. Samples of Au, Co, and Au-Co deposited oa stainless steel wool (SSW), stainless steel coupons (SSC), copper coupons (CC), and bronze eoupons (BC) were exposed 10 Ying vapor from a Zine source ata temperature of 380° C. ‘nd material containing the nanoparices ata temperatore ‘f 350°. sing a high vacuum thermal deposition apparatus Samples were exposed to zine vapor from a high vacunm thermal deposition apparatus. The zine vaporization and filer temperature conditions were 380° C. and an initial vacuum pressure of atleast Sx10°* Torr TFIG. 1 provides images of the nanoparticle treated SSW before (a) and after (b) exposure to zine vapor. FIG. 1 also provides images of the untreated bronze pellets before (e) ‘nd after (2) zine exposure Visual examination indicates that nanoparticle tated SSW exposed to zine vapor did not reveal any change color, unlike the bronze peles (initially orangerbronze and thea 2 golden tinvbrass alter zine alloying). ‘As illustrated in FIG. 2, visual examination of the copper ‘eoupons, stainless steel coupons, and bronze coupons shows ‘significant color change after gold nanoparticle deposition ‘nd exposure to Zine vapor. The first row of FIG. 2 provides mages of the substrates without nanoparticle deposition. The second row of FIG. 2 provides images ofthe substates, US 9,700,829 BI 9 with gold nanoparticle deposits but before exposure to zine vapor, The third row of FIG, 2 provides images of the substrates with gold nanopartele deposits and after exposure to zine vapor. All samples were examined using. Scanning Fleetron Microscopy (SEM) and Energy Dispersive X-Ray Spectros- ‘copy (EDX). The examples were analyzed to evaluate the celletiveness of the materials as zine getters ‘Semi-quantitative analysis was conducted on the sample as well as X-ray mapping (PIG. 3). In panicular, FIG. 3a shows. an EDX mapping analysis of gold nanoparticles deposited onto stainless steel wool after zine deposition, FIGS. 3) and 3e provide SEM images showing zine deposits ‘on the gold nanoparticles EDX microanalysis of Au, AuCo and Co nanopanicles before and aller Zn exposure was performed to evaluate nanoparticle composition of mono and bimetallic colloids (FIG. 3a). The EDX mapping analysis demonstrates the location of the elements of inteest: Au, Co, and Zn. The ‘chemical analyses for the zine exposed samples are listed Table I TABLE | ‘Conpostion of Deposits Biol on San Quasisive Kray » no As shown in FIGS. 4, 5, and 6, the SEM analysis shows that nanoparicle treed SSW materials are elective Za cr motels PGs. 4 provider SEM images of aanopare les poi onto lenge] woo fre an ai {ine vopor exposure FIC. 8 provides SEM images of fanoparteles deposited onto various subsites helore and fer vine vapor exposure. Ths fist row of FIG. § provides Serf io ee wool wiht nny 06 eri nobles bee od ses vopr ponies Th aditon, th sie deposits could be cai observed on samples exposed to Zine Vapor. Large scale nanoparticles and micrseale zine pariclates were detect. Alter zine fexponure, sibstrter modified with nanoparticles show nanoparticle sintering effets because these experiments ‘were condicted at high temperatures. Sintering may be beneficial de tothe inersaselasion propertiss which may Keep the nc deposits llached 10 the subsites Fimlikenanodeposits were also observed, Without fend ing to be limited by theory, tis believed that during the deposition process zine i (a) captured an alloy when seized or tapped by nanoparticles and (b) forms individ large zine rectangular seus. 10 The deposits that appear to have increased in size inere- ‘mentally with the relative size changes are shown in FIG. 7 Inpartcula, FIG. 7 shows the nanoparticle sizes belore zine sition and after zine deposition, For the Au—Co alloys before zinc exposure, dserete particles having an average size of around 30 nn and nanoparticle clusters having an average size of around 128 nm were observed. After Zine ‘exposure, the nanoparticles increased in size. For instance, the average ofthe nanoparticles was approximately 38 tm, ‘while nanoparticle clusters had a bimodal distribution (eg. average siaes of 134°nm and 336 nm). The results are Indicated in Table 2 TABLE 2 rage Sasso ad Ate Zine Expose umpuite Dion Pp) tp a TABLE 2-omtinied ” Sorat ar wuwpiie Datu Bovina) Btn a « “ = s oo a ‘When analyzed by EDX, it was determined that gold nanoparticles on sailess steel wool were etter Zine peters US 9,700,829 BI uw followed by Au—Co cone-shell, AU-Co alloy, and Au— ‘CoCo alloy/corelshell FIG. 82). When using cobalt based nanoparticles on stainless steel wool, it was determined that the Au--CoCo alloy’eorelshell nanopanicles were beter ine getters followed by Au-Co core-shell and Co nano- Particles (FIG. 85). ‘When nanoparticles were deposited onto substrates and ‘evaluated as zine getters, a mass increase was recorded (measured on an analytical scale balance), demonstrating ‘once again thatthe materials and nanoparticles are elfetive ‘ine getter materials, This inerease in mass is indicated in Table 2 TABLES Mas Caage Ales Zs Vigor Fag See Aer Zine Espo 72 By ha ba 03 ha he 1s on ta as na sume Ineo fico se ‘uta ae (mi) ‘tee Oba Annet fn take i—tose Anas In the table above, when referring to time, such time indicates the time of growth of the nanoparticles on the metal substratelsupport. When the time of growth was Jonger it was observe that such nanoparticles were capable ‘of eapturingtraping’gtting more zn, as evidenced by the Jnereased change in mass, Without intending to be limited by theory it is believed that such increase isd to the inrease in size of the nanoparticles andor greater deposition/srface tea coverage of the nanoparticles on the metal substrate In addition, for further metal quantitation, inductively ‘coupled plasma atomic emission spectroscopy’ (ICP-MS) was also performed (FIGS, 90-90), The data Was analyzed and determined to bein agreement with the FDX analysis and showing/eonfirming the attachment of the nanoparticles, ‘on the substrate FIG. 10 provides SEM images of 1 material containing nanoparticles on stainless steel wool after exposure to zine vapor and sonication in water. According tothe images, the 0 o 12 nanoparticles stayed on the substrates even after 60 minutes fof sonication while the zine was predominantly removed trom the subsirats after sonication. X-ray powder diffaction (XRD) (PIG. 11) data was collected on materials containing gold nanoparticles on Stainless stel coupons exposed to zine vapor. The data ‘hows that gold nanopanieles alloy with the zine vapors and form an intermetallic compound. The alloying of the gold ‘nanoparticles with zine was confiemted by the disappearance of the Au(IL1) peak and the emergence of two AUsZa, iaetion peaks (021) and 221). In this regard, upon alloying, gold peaks can be observed at a diffraction angle (28) of 21° and/or 221°, Alloying can be indicative of the ‘material's sahility and getering capability Tis written description uses examples to disclose the ‘vention, including the best mode, and also to enable any person skilled in the art to practice the invention, including ‘making and using aay devices or systems and performing any incorporated methods. ‘The patentable scope of the invention is defined by the claims, and may inelude other fexamples that occur to those skilled in the art. Such other ‘examples are intended to be within the scope of the clams $f they inclade stmctal elements that do not differ from the Titra language ofthe claims, or if they include equivalent structural elements with insubstantial differences from the Tera languages ofthe claims. ‘he invention claimed is: 1. A method of capturing oF trapping zine, the method comprising ‘contaeting a zine vapor with a zine getter material com= ‘ising nanoparticles and a metal substrate 2. The method according to claim 1, wherein the zine ‘vapor comprises a zine ridisisotope. 3. The method according to claim 1, wheres ‘vapor comprises zine, 4. The method sevording to claim 1, wherein the nano- particles comprise cobalt, gold, or a combination theroo. 5. The method aecording t claim 1, wherein the nano- particles comprise cobalt and gold 6. The method aecording to claim 1, wherein the nano- particles have a core-shell configuration, 7. The method according to claim 1, wherein the nano- particles comprise # metal alloy 8. The method aevording ( claim 1, wherein the metal substrate comprises copper, tin, chromium, ora combination thereat: 9. The method aecorting t claim 1, wherein the metal substrate comprises copper, a bronze, or a stainless ste! 10. The method aecording to claim 1, wherein the nano- particles form diserete particles on the metal substrate 11. The method according to claim 1, wherein the nano- particles cover from 5% 10 90% ofthe surface area of the ical substrate 12, The method according to claim 1, wherein before the contcting sep, the nanoparieles have an average particle Size of from 3 nm to 500 nm, 13. The method according to claim 1, wherein before the ‘contacting step, the nanoparticles having s multimodal size ‘istrbution. 14, The method sccording to claim 13, wherein the nanoparticles have frst size distibution having an average size of from 2 nm to $0 nm and a socond size distribution having an average size of fom greater than 50 nm to 150 18. The method according to claim 1, wherein after the contzeting step. the nanoparticles have ® multimodal size

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