Anodes of 304 stainless steel have been processed by a continuous wave Yb fiber laser with a wavelength of 1.064 μm and subjected to 50 keV electron bombardment in order to determine the extent to which hydrogen outgassing is reduced by the laser surface melting treatment. The results show a reduction in outgassing, by approximately a factor of four compared to that from untreated stainless steel. This is attributed to a reduction in the number of grain boundaries which serve as trapping sites for hydrogen in stainless steel. Such laser treated anodes do not require post-processing to preserve the benefits of the treatment and are excellent candidates for use in high power source devices.Work supported by US Air Force contract FA8650-11-D-5401 at the Materials & Manufacturing Directorate (AFRL/RXAP). The authors thank Lt Col Victor Putz of AFOSR/EOARD and Jason Marshall at AFOSR.D.G and M.S. wish to thank the EPSRC (EP/K503241/1)

Back, TC

Cahay, MM

Fairchild, SB

Gortat, D

Gruen, GJ

Lockwood, NP

Murray, PT

O'Neill, W

Sparkes, M

D. Gortat

P.T. Murray

S.B. Fairchild

M. Sparkes

T.C. Back

G.J. Gruen

M.M. Cahay

N.P. Lockwood

W. O'Neill

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Materials Letters

Laser surface melting of stainless steel anodes for reduced hydrogen outgassing

Apollo (Cambridge)

Materials Letters 190 (2017) 5–8Contents lists available at ScienceDirectMaterials Lettersjournal homepage: www.elsevier .com/locate /mlblueLaser surface melting of stainless steel anodes for reduced hydrogenoutgassinghttp://dx.doi.org/10.1016/j.matlet.2016.12.1010167-577X/Crown Copyright  2016 Published by Elsevier B.V.This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).⇑ Corresponding author.E-mail address: dg458@cam.ac.uk (D. Gortat).D. Gortat a,⇑, P.T. Murray b, S.B. Fairchild c, M. Sparkes a, T.C. Back b, G.J. Gruen b, M.M. Cahay d,N.P. Lockwood e, W. O’Neill aa Institute for Manufacturing, University of Cambridge, 17 Charles Babbage Road, Cambridge CB3 0FS, UKbResearch Institute, University of Dayton, Dayton, OH 45469, USAcAir Force Research Laboratory, WPAFB, OH 45433, USAd Spintronics and Vacuum Nanoelectronics Laboratory, University of Cincinnati, Cincinnati, OH 45221, USAeDirected Energy Directorate, Air Force Research Laboratory, Kirtland, AFB, NM 87117, USAa r t i c l e i n f oArticle history:Received 1 June 2016Received in revised form 11 December 2016Accepted 28 December 2016Available online 29 December 2016Keywords:Grain boundariesLaser processingMetals and alloysVacuum electronicsHydrogenOutgassinga b s t r a c tAnodes of 304 stainless steel have been processed by a continuous wave Yb fiber laser with a wavelengthof 1.064 lm and subjected to 50 keV electron bombardment in order to determine the extent to whichhydrogen outgassing is reduced by the laser surface melting treatment. The results show a reductionin outgassing, by approximately a factor of four compared to that from untreated stainless steel. Thisis attributed to a reduction in the number of grain boundaries which serve as trapping sites for hydrogenin stainless steel. Such laser treated anodes do not require post-processing to preserve the benefits of thetreatment and are excellent candidates for use in high power source devices.Crown Copyright  2016 Published by Elsevier B.V. This is an open access article under the CC BY license(http://creativecommons.org/licenses/by/4.0/).1. IntroductionHigh Power Source (HPS) devices are used in numerous applica-tions including vacuum electronics [1–3], particle acceleration[4,5], and microwave generation [2,6]. Stable, long term HPS oper-ation is presently constrained by pulse shortening due to plasmaformation in the anode-cathode gap region. Plasma is formedthrough the interaction of secondary electrons and gas molecules(primarily hydrogen), both of which are released by the impactof high energy electrons at the anode surface. Metals with rela-tively low hydrogen outgassing rates, such as austenitic stainlesssteel (SS) [7], are the most commonly used materials for vacuumapplications [7]. To further reduce outgassing in such metals, sev-eral treatments have been proven effective including baking [8–12], vacuum baking [8,11,13,14], polishing [8,14], and surfacetreatments to create oxide or other protective surface films. Elec-tropolishing has been the method of choice [8,11,15] since it bothreduces the surface roughness of anode materials and creates anoxide layer that further reduces hydrogen outgassing. However,electropolishing may also introduce hydrogen and other contami-nants into the surface layers in significant quantity [15] and maynecessitate an additional bake to thoroughly degas the surface [8].The purpose of the work described here was to determine thefeasibility of reducing hydrogen outgassing by processing anodesof 304SS by laser surface melting (LSM). The LSM processing tech-nique entails irradiating a sample with the output of a high energycontinuous laser beam, thereby causing melting, flow and re-solidification of the material as the laser beam is scanned acrossthe sample surface. This process has the potential of reducing out-gassing by forming a more crystalline layer (with fewer grainboundaries), thereby reducing the number of potential sites thatcan trap hydrogen in the metal [16]. When compared to more con-ventional processing techniques, such as electropolishing, the LSMprocess introduces significantly fewer contaminants (especiallyhydrogen) into the anode surface. We show here that LSM process-ing of 304SS does indeed lead to reduced H2 outgassing duringelectron bombardment.2. ExperimentalSamples of 304SS were irradiated at normal incidence by a non-polarized Continuous Wave (CW) SPITM G3 Yb fiber laser (M2 = 2,input beam diameter 4.3 mm), with a wavelength of 1.064 lm,6 D. Gortat et al. /Materials Letters 190 (2017) 5–8maximum output power of 20 W and nominal spot size of 39.4 lm.The treatment was carried out at atmospheric pressure under con-stant N2 flow into the capped stage (O2 levels <0.2%), as shown inFig. 1. The beam expander telescope (BET) supplied an input beamof 4.3 mm in diameter to the laser head.The lens used in the laser setup was a JenopticTM fused silica lenswith focal length of 125 mm. For patterning the sample, a bidirec-tional raster scan was applied with a line separation of 30 lm andirradiated with a average laser energy density (ED) of 13.54 kJ/cm2.Additional details of the LSM processing can be found elsewhere[17]. An Olympus BX51TM optical microscope with JENOPTICTM Pro-gResC10+CCD camera was used to obtain images and depth mea-surements of the treated samples. For the depth measurements,the SS samples were cut along the laser-scanning track andmechanically polished using standard metallographic techniques.The samples were chemically etched in SS micro-etchant, chemicalcomposition 10 g FeCl3 30 ml HCl 120 ml water, at room tempera-ture to reveal the general microstructure. Scanning electron micro-scopy (SEM) images were acquired with a FEITM Quanta 3D systemequipped with a field emission gun (FEG). Microstructural charac-terization was conducted with the help of focused ion beam (FIB)microscopy and Philips XL30 SEM with FEG in secondary electronmode to obtain orientation maps. HKLTangoTM software was usedto quantify the grains and grain boundaries (GBs). GBs were cate-gorized in two groups, special (3 <P6 29) and random(29 <P6 49), wherePis the reciprocal of the fraction of the com-mon lattice sites (CSL) from each grain at the boundary [18]. Morerestrictive Palumbo-Aust criterion [19] is used to determine thePnumber.Outgassing characterization was carried out by bombarding atnormal incidence the SS samples with the focused output of a50 keV electron beam with a spot size of 1.6 mm in diameter(determined by measuring the size of a hole formed in a thin Ni foilunder conditions identical to those used for the present work) with60 s duration current pulse, and recording the time evolution dur-ing the pulse of the H2 signal with a residual gas analyzer situated45 degrees from the surface normal. The electron current densityat the sample surface was approximately 16.4 mA/cm2, and thebase pressure was 5  1010 Torr.3. Results & discussionIn order to form samples for depth characterization and out-gassing evaluation, the SS samples were processed by raster scan-ning the laser beam across the surface in a uniform pattern. Shownin Fig. 2a is an SEM image of the raster scanned surface of the SSsample, tilted at 45 degrees to the electron beam column; theLSM-treated and untreated areas are visible. The individual lasertracks can be seen as can the ripples within each track that are ori-Fig. 1. Laser processing workstation showing the Yb fiber laser, Isolator forpreventing unwanted feedback into the laser, BET, nitrogen supply and samplestage.ented in the direction of the laser beam scan; a phenomenon in CWlaser melting commonly observed at high laser ED values [20]. Pro-cessing with lower ED tends to avoid ripple formation in the irra-diated area but also reduces grain growth in the lattice of thesample. There are also small, bump-like formations seen withinthe treated area. Note that the features extend above the plane ofthe laser treated area and occur near the overlap between adjacentlaser scan lines. These features represent areas of the SS surfacemorphology that were incompletely melted by LSM and mostlikely result from the specific choice of scan parameters (laser spotsize and degree of overlap between adjacent scan lines) for theresults shown here. These features can be minimized by a differentchoice of initial scan parameters or by subsequent laser passes overthe sample. Shown in Fig. 2b is a longitudinal cross-section (opti-cal) view of the treated sample, where the treated region is com-prised of an LSM zone (LSMZ) and heat-affected zone (HAZ). Thedepth of the LSMZ is approximately 9.7 lm.Shown in Fig. 3a and b are FIB images of the untreated and trea-ted samples, respectively, demonstrating the microstructuralchanges induced by the laser radiation. It can be observed thatthe grains in the laser treated area, Fig. 3b, are elongated in thedirection of the laser scan and have increased in size as a resultof laser processing, as detailed in Table 1. The total number ofgrains was reduced from 1020 to 617 per 0.12 mm2 unit volume.This transformation has the net effect of reducing the number ofspecial and random GBs in the laser-treated volume and supportsthe outgassing data showing less H2 released from such samples.Table 1 suggests that it is the grain boundary character distribu-tion, i.e., the spectrum of misorientations and inclinations whichis changed as a result of laser melting. Increasing further the grainsize would entail extending the surface cooling time [21]. In fact, asshown in Fig. 2, during laser melting only the thin surface layer ismelted which then rapidly solidifies due to the high heat outflowtoward the solid substrate. Therefore, we believe that in our casethe spectrum of misorientations and inclinations corresponds toa temperature close to the melting temperature Tm. However, itis well known that the equilibrium grain boundary character distri-bution changes significantly with temperature [22,23]. Forinstance, in conventional solidification, the temperature actuallydecreases slowly, and the spectrum of grain boundary misorienta-tions and inclinations corresponds to a lower temperature of about0.5 Tm. To optimize the reduction of hydrogen outgassing fromstainless steel anodes using the laser surface treatment reportedhere, a more thorough analysis would require a study of the grainboundary character distribution as a function of the laser spot sizeand energy density [22,23].Shown in Fig. 4 are the outgassing results, which are presentedas the change in H2 partial pressure (above baseline) with electrondose. Both curves exhibit an increase in H2 signal with electrondose. Note that the H2 signal for the untreated sample does notimmediately rise with electron dose but instead shows an incuba-tion period (extending from a dose of 0 to 3  1018 cm2) inwhich the H2 signal first increases gradually, after which there isa more rapid, nonlinear increase. Hydrogen is present within manymetals, where it exists as atomic H at defects such as GBs [16];Hydrogen outgassing from metals occurs [24] through a series ofsteps consisting of (a) diffusion of atomic H to the metal surface,(b) recombination of atomic H at the surface and (c) desorptionof nascent, molecular hydrogen H2 into the gas phase. The incuba-tion period most likely is comprised of step (a) in which the major-ity of incident electron flux goes toward heating the sample andenhancing H atom diffusion to the surface. Only after the inductionperiod is there sufficient atomic H at the surface that steps (b) and(c) proceed more efficiently and a larger desorbed H2 signal isdetected. The data from the LSM-treated sample exhibits a smallerinitial slope, suggesting a lower rate of diffusion of atomic H to theFig. 2. (a) SEM image of the raster scanned SS sample with ED of 13.54 kJ/cm2 tilted at 45 degrees to the electron beam column emphasizing the bump-like features and theiroccurrence at the overlap of laser scan lines, the arrows show the direction of the laser raster, and (b) optical micrograph of the section view showing the depth of the treatedregion.Fig. 3. FIB image showing the microstructure of the (a) untreated and (b) treated SS sample. The arrows show the direction of the laser raster.Table 1Grain boundary character distribution per 0.12 mm2 surface area.Position R3 R9 3 <P6 29 29 <P6 49 Average grain size (lm) Average grain area (lm2)Base material 33.81 1.43 35.11 0.07 10.72 99.88LSMZ 15.39 0.82 16.66 0.05 14.12 201.59Fig. 4. Outgassing results showing the change in H2 partial pressure with electrondose during 60 s electron irradiation.D. Gortat et al. /Materials Letters 190 (2017) 5–8 7surface because of the decreased number of GBs. The differences inthese data sets are currently being investigated in more detail.The data indicate that H2 outgassing from the LSM-treated sam-ple was approximately a factor four less than that from theuntreated SS sample, for the conditions employed here.4. Conclusions304SS treated with CW, non-polarized Yb fiber laser radiation atan ED value of 13.54 kJ/cm2 showed reduced hydrogen outgassingby a factor of 4 at an electron dose of 6  1018 cm2, indicatingthe feasibility of the LSM process for reducing hydrogen outgassingfrom SS anodes. Such laser treated anodes do not require post-processing to preserve the benefits of the treatment. The mecha-nism of suppression of hydrogen outgassing is caused by stimulat-ing grain growth in the lattice of the specimen. Further studies areplanned to maximize hydrogen outgassing reduction via grainboundary character distribution as a function of the laser spot sizeand energy density.8 D. Gortat et al. /Materials Letters 190 (2017) 5–8AcknowledgmentsWork supported by US Air Force contract FA8650-11-D-5401 atthe Materials & Manufacturing Directorate (AFRL/RXAP). Theauthors thank Lt Col Victor Putz of AFOSR/EOARD and Jason Mar-shall at AFOSR.D.G and M.S. wish to thank the EPSRC (EP/K503241/1).References[1] K.E. Hackett, Directed Energy Applications for High Power Vacuum Electronics,Vac. Electron. Conf. 2006 Held Jointly with 2006 IEEE Int. Vac. Electron Sources,IEEE Int. 2006 (2006) 11–13.[2] R.J. Barker, E. Schamiloglu, High-power microwave sources and technologies,Wiley-IEEE Press, 2001.[3] J.H. Booske, R.J. Dobbs, C.D. Joye, C.L. Kory, G.R. Neil, G.S. Park, et al., Vacuumelectronic high power terahertz sources, IEEE Trans. Terahertz Sci. Technol. 1(2011) 54–75.[4] S.D. Korovin, V.V. Rostov, S.D. Polevin, I.V. Pegel, E. Schamiloglu, M.I. Fuks,et al., Pulsed power-driven high-power microwave sources, Proc. IEEE 92(2004) 1082–1094.[5] D. 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Laser surface melting of stainless steel anodes for reduced hydrogen outgassing

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