national institute of research and development for … 2005... · 2017. 12. 27. · water...

ROMANIAROMANIA

NATIONAL INSTITUTE NATIONAL INSTITUTE OF RESEARCH AND DEVELOPMENT OF RESEARCH AND DEVELOPMENT

FOR CRYOGENICS AND ISOTOPE FOR CRYOGENICS AND ISOTOPE TECHNOLOGIESTECHNOLOGIES--RM VALCEARM VALCEA

Water detritiation. Endurance test for theWater detritiation. Endurance test for thecatalystcatalyst--packing mixture for water packing mixture for water

detritiation system at JET. Permeability of detritiation system at JET. Permeability of tritium into different materials as a function tritium into different materials as a function

of partial pressure, temperature and of partial pressure, temperature and concentrationconcentration

INCINC--DTCI ICIT DTCI ICIT Rm. ValceaRm. Valcea

NATIONAL R&D INSTITUTE FOR CRYOGENICS AND ISOTOPES TECHNOLOGIES ICIT RM. VALCEA

GENERAL PRESENTATION OF ICITGENERAL PRESENTATION OF ICIT

MAIN ACTIVITIESMAIN ACTIVITIES::

Equilibrium research and isotopes separation (tritium, Equilibrium research and isotopes separation (tritium, deuterium), including industrials pilot plants level;deuterium), including industrials pilot plants level;

Equilibrium research and gases separation process, purification Equilibrium research and gases separation process, purification technologies and highly recuperative system;technologies and highly recuperative system;

Cryogenic installation and technologies for separation, Cryogenic installation and technologies for separation, purification and gases liquefaction (argon, helium, hydrogen, purification and gases liquefaction (argon, helium, hydrogen, carbon dioxide, nitrogen, oxygen);carbon dioxide, nitrogen, oxygen);


ROMANIA

GENERAL PRESENTATION OF ICITGENERAL PRESENTATION OF ICIT

MAIN ACTIVITIESMAIN ACTIVITIES::

Technologies for heavy water separation, technical analysis and Technologies for heavy water separation, technical analysis and tritium analysis;tritium analysis;Turbo molecular pumps, vacuum accessories, membranes Turbo molecular pumps, vacuum accessories, membranes compressors, cryogenic pumps;compressors, cryogenic pumps;Heavy water etalons, depleted water;Heavy water etalons, depleted water;Risk studies for chemical and petrochemical plants;Risk studies for chemical and petrochemical plants;Static and dynamic equilibration analysis.Static and dynamic equilibration analysis.


ROMANIA

Cryogenic Resilience Experimental StandCryogenic Resilience Experimental StandNATIONAL R&D INSTITUTE FOR CRYOGENICS AND ISOTOPES TECHNOLOGIES

ICIT RM. VALCEA

Deuterium Depleted Water Laboratory Gas Mixtures LaboratoryNATIONAL R&D INSTITUTE FOR CRYOGENICS AND ISOTOPES TECHNOLOGIES

ICIT RM. VALCEA

SEPARATION TECHNOLOGIES FOR HYDROGEN ISOTOPES. SYSTEM FOR

TRITIUM EXTRACTION FROM TRITIATED HEAVY WATER

(TWO-TRIT/REM)

(2000-2001)


ROMANIA

EURATOM PROGRAM

SEPARATION TECHNOLOGIES FOR HYDROGEN ISOTOPES. SEPARATION TECHNOLOGIES FOR HYDROGEN ISOTOPES. SYSTEM FOR TRITIUM EXTRACTION SYSTEM FOR TRITIUM EXTRACTION

FROM TRITIATED HEAVY WATERFROM TRITIATED HEAVY WATER(TWO(TWO--TRIT/REM)TRIT/REM)

OBJECTIVES:OBJECTIVES:

Comparative Comparative studystudy of of thethe catalystscatalysts utilisedutilised in in isotopicisotopic catalystcatalyst exchgangeexchgange;;AnalysisAnalysis methodmethod for for hydrogenhydrogen isotopesisotopes; ; SpeciesSpecies distributiondistribution of of tritiumtritium in in multicomponentmulticomponentmixturesmixtures;;SecuritySecurity arhitecturearhitecture for for tritiumtritium processingprocessing plantsplants..



Performed TasksPerformed TasksExperimental facility "System for Tritium Removal from Water" Experimental facility "System for Tritium Removal from Water" by catalytic isotope exchange waterby catalytic isotope exchange water--hydrogen and/or hydrogen and/or deuterium and cryogenic distillation of hydrogen and its deuterium and cryogenic distillation of hydrogen and its isotopes;isotopes;Software for designing and simulation the behavior of a Software for designing and simulation the behavior of a system for catalytic isotope exchange tritiated water system for catalytic isotope exchange tritiated water --hydrogen and deuterium;hydrogen and deuterium;Comparison of isotope exchange catalysts manufactured at Comparison of isotope exchange catalysts manufactured at FZK FZK KarlsruheKarlsruhe and ICIS Rm. Valcea;and ICIS Rm. Valcea;Comparatively determination of efficiency and pressure drop Comparatively determination of efficiency and pressure drop for ordered and disordered packages.for ordered and disordered packages.



Experimental facilityExperimental facility--LPCE columnLPCE column

--CondenserCondenser

--BoilerBoiler

--Equilibrator HEquilibrator H--DD

OPTIMISATION OF THE RATIO PACKAGE/CATALYST FOR THE

SIMULTANEOUSTRANSFER OF TRITIUM AND DEUTERIUM IN A WATER

DETRITIATION FACILITY(JW0-FT-2.1)

(2001 – 2002)


ROMANIA

EURATOM PROGRAM

OBJECTIVES:

To manufacture ordered packages with different size and catalysts of different size and composition with higher surface area for gas-vapor-liquid exchange;To establish the influence of deuterium transport on tritium transport when the two processes take place simultaneously;The model related to deuterium transport will be developed to include also the tritium transport, i.e. the transfer all three hydrogen isotopes will be followed;To establish the correlation between the required ratio package to catalyst in different working conditions: flow rates of gas, vapors and liquid in order to maximize the isotopic transfer for a specified height of column.


OPTIMISATION OF THE RATIO PACKAGE/CATALYST FOR OPTIMISATION OF THE RATIO PACKAGE/CATALYST FOR THE SIMULTANEOUSTRANSFER OF TRITIUM AND THE SIMULTANEOUSTRANSFER OF TRITIUM AND DEUTERIUM IN A WATER DETRITIATION FACILITYDEUTERIUM IN A WATER DETRITIATION FACILITY

The influence of geometrical characteristics of ordered The influence of geometrical characteristics of ordered package/catalyst on the separation performances for two package/catalyst on the separation performances for two diameters of isotopic exchange column: 40 mm and 100 mm;diameters of isotopic exchange column: 40 mm and 100 mm;The separation performances were verified for specified The separation performances were verified for specified working conditions of temperature, flow rates of gas, vapor working conditions of temperature, flow rates of gas, vapor and liquid, as well as the ratio of package/catalyst;and liquid, as well as the ratio of package/catalyst;Influence of deuterium transport on tritium transport when the Influence of deuterium transport on tritium transport when the two processes take place simultaneously in the catalytic two processes take place simultaneously in the catalytic isotopic exchange column.isotopic exchange column.



FROM TRITIATED HEAVY WATERFROM TRITIATED HEAVY WATER(TWO(TWO--TRIT/REMTRIT/REM

Studies:Studies:

ExperienceExperienceExperience in projecting and technology Experience in projecting and technology process of heavy water separationprocess of heavy water separationExperience in process of catalyse and mass Experience in process of catalyse and mass and heat transferand heat transferTechnological transfer and implementing to Technological transfer and implementing to ROMAG Drobeta;ROMAG Drobeta;Technical assistance for heavy water industrial Technical assistance for heavy water industrial plantplantExperience in developing of isotopic exchange Experience in developing of isotopic exchange and cryogenic distillation technologyand cryogenic distillation technologyPerformed laboratory systems and equipmentPerformed laboratory systems and equipment

ENDURANCE TEST FOR THE CATALYSTENDURANCE TEST FOR THE CATALYST--PACKING PACKING MIXTURE PROPOSED FOR WATER DETRITIATION MIXTURE PROPOSED FOR WATER DETRITIATION

SYSTEM AT JET USING SCKSYSTEM AT JET USING SCK--CEN MIXTURECEN MIXTURE

GHEORGHE IONITA, ANISIA BORNEA, IOAN STEFANESCU, NICOLAE BIDICA, IRINA POPESCU, CARMEN VARLAM

National Institute for Cryogenics and Isotopic Technologies (ICIT), Rm. Valcea

JOHAN BRAET-SCK- CEN Mol, Belgium

CRISTIAN POSTOLACHE and LIDIA MATEI National Institute for Physics and Nuclear Engineering (IFIN H-H) - Bucharest

- ICSI Romania EFDA JET Technology Workprogramme 2004 JW4-FT-2.20 Task

- CEN- Belgium

WATER DETRITIATION SYSTEM (WDS)

* The Water Detritiation System (WDS) is based on an enrichment of the tritiated water inside a Liquid Phase Catalytic Exchange (LPCE) column, then a dissociation of oxygen and hydrogen isotopes in an electrolyser and the separation of the hydrogen isotopes inside a cryogenic distillation (CD) column and Gas Chromatography (GC)

*The main requirements for the design of a WDS for JET are:- to process 10 tons tritiated water of ~ 1Ci.kg-1 during one operation campaign of 2-3 months,- to achieve a decontamination factor of 104 along the stripping section of the LPCE column to deliver a tritium content in bottom product of CD column in the range of 0.5-1% atomic ratio to allow further separation by the GC systems.

LIQUID PHASE CATALYTIC EXCHANGE (LPCE)

* The key point of WDS is LPCE column, based on isotopic exchange process between hydrogen and water. At ambient temperature isotope transfer is very low and need a catalyst. In practice a mixture of hydrophobic catalyst and hydrophilic packing promotes the process.

* HT +H2O (v) <-->H2 + HTO(v)H20 (v) + HTO (l)<--> H2O (l) +HTO (v)HT+HTO (l) <--> H2 + H2O

* Conventional hydrophilic catalysts loose their activity in contact with liquid water and water vapor because of the low solubility of hydrogen in liquid water. Hydrophobic catalysts have high a good catalytic activity and high stability and could avoid such disadvantages. For this purpose, over 100 hydrophobic catalyst types have been prepared and tested

TABLE 1. The main types of hydrophobic catalysts and mixed packing tested and selected for tritium removal by H2-H2O isotopic exchange

COUNTRY

Tested catalyst types and metal content (wt%)

Selected catalyst type and its stability

The type of selected mixed packing

CANADA

0.5%- Pt / Al2O3 0.4%- Pt / PTFE 0.1-0.4%- (Pt / C)/PTFE (emulsion) Pt / zeolite Pt / SiO2

0.1% - (Pt/C)/PTFE After 170 days running the catalyst lost 13 % off initial activity

1) A matrix of platinized hydrophobic carbon and PTFE deposited on corrugated screening and wound with alternate layers of hydrophilic cotton cloth 2) Random packing consisting of 50% 0.37% Pt/C PTFE catalyst and 50% hydrophilic packing

INDIA

1% - (Pt /C)/PTFE 1% - (Pt/Al2O3)/PTFE 1% - (Pt/zeolite)/PTFE

1% - Pt/C/ PTFE Minimum some weeks

-

JAPAN

1.5% - Pt/PTFE 0.1-2% - Pt/SDBC 1.2-1.4% - Pt/SDBC-film type Pt /FC-PTFE Pt/Al2O3

0.5% - Pt/SDBC (Kogel catalyst) 13 years in separated bed reactor process without any regeneration

1) Separated beds of 0.5%Pt/SDBC catalyst and Mac Mahon hydrophilic packing in which the liquid water is not in contact with the catalyst. 2) 1.5%Pt/PTFE rings (7 x 3 x 0.8 mm) and mists water (particle size 5 mm) in con-current with H2 gas

GERMANY 0.4% - Pt/C/PTFE 0.4% - Pt/C/PTFE - ROMANIA

0.1-1% - Pt/C/PTFE 0.1-2% - Pt/SDB 0.1-2% - Pt/SDB/PS 0.5% - Pt/SDB/PTFE

0.45% - Pt/C/PTFE One year half in LPCE process, without any regeneration

Alternated beds of 0.45% Pt/C/PTFE and thermo-chemical activated metal hydrophilic packing

BELGIUM

Pt; Pd; Ni; Pt-Ni; Pt-Pd; deposited on carbon or TEFLON (over 30 different types)

1% - Pt/C/ PTFE 5000 hours

67% etched Dixon packing and 33% Pt/C /PTFE

catalyst

RUSSIA

0.8% - Pt/Polysorb Pd/Al2O3

0.8% - Pt/Polysorb

Alternated beds of granulated platinum / Polysorb catalyst and hydrophilic metallic packing (Levin’s packing)

U.S.A

0.1% - Pt/C/PTFE (Canadian catalyst)

0.1% - Pt/C/PTFE

Ordered packing consisting of Pt/C/PTFE dispersed on corrugated stainless steel screen mesh with a cotton fabric overlaid on the screen and wound in a cylindrical shape.

PRESENT STATUS

• Laboratory experiments were carried out to investigate the separation performances of different catalysts and catalyst/packing mixtures • The separation performances have been measured against several parameters: the operating temperatures (40 to 80°C), the composition of the catalysts (platinum concentration and ratio between the support materials), catalyst particle size, type of packing (etched stainless steel or phosphoro-bronze), catalyst /packing filling ratio and the mixing mode between catalyst and packing (homogenous or layers).• Two catalyst/packing mixtures, which have both good technological behavior and separation performances, were selected for further investigations and improvements.

a)SCK - CEN packing;b)FZK-ICIT packing.

Characteristics of the two selected mixturesMixture A Mixture B

Pt: 1%wC: 19%wPTFE: 80%w

Pt: 1.5%wC: 15%wPTFE: 83.5%w

Pellets PelletsCatalyst

Ø=1.9mm x2mm Ø=2mm x 4mmMinispirals Wire mesh

Stainless steel Stainless steelPackingØ=2mm x 2mm

Filling ratio(catalyst/packing)

1:2homogeneous

1:2.5sandwich method

Temperature 40°C 60-80°CColumn diameter 20 mm 38 mm[T] in H2 inlet stream 100 kBq/mol -[D] in H2 inlet stream 50 ppm 1-2 %G/L 3.51 3.35HETP (cm) 11.38 26

* The both mixed packing are based on Pt/C/PTFE catalyst and have closed performances but their catalytic stability at exposure to b-tritium radiation have to be very well known.* The separation performances, assessed with the height equivalent of theoretical

plates (HETP), are highly dependent on the ration G/L between the specific molar flow rates of hydrogen and water

THE GOAL OF THE PROJECTTHE GOAL OF THE PROJECT

The main purpose of project is to study:The main purpose of project is to study:∗∗ influence of tritium influence of tritium ββ--radiation and of impurities on SCKradiation and of impurities on SCK--CEN CEN catalyst/ packing mixturecatalyst/ packing mixture’’ performances in LPCE process;performances in LPCE process;∗∗ influence of tritium influence of tritium ββ--radiation and of impurities on radiation and of impurities on physicophysico--structural parameters of materials from SCKstructural parameters of materials from SCK--CEN mixed catalytic CEN mixed catalytic packing;packing;∗∗ stability in time of SCKstability in time of SCK--CEN catalytic mixed packingCEN catalytic mixed packing’’performances;performances;∗∗ procedure for regeneration of catalyst and the activation of Sprocedure for regeneration of catalyst and the activation of SCKCK--CEN packing;CEN packing;∗∗ erosion and mechanical resistance of SCKerosion and mechanical resistance of SCK--CEN packing in LPCE CEN packing in LPCE process;process;∗∗ identification of potential poisons for Ptidentification of potential poisons for Pt--hydrophobic catalyst in hydrophobic catalyst in hydrogenhydrogen--water LPCE process.water LPCE process.

EXPERIMENTAL PROTOCOLEXPERIMENTAL PROTOCOL

∗∗ Endurance tests for SCK Endurance tests for SCK –– CEN packing will be performed CEN packing will be performed for 3, 6and 9 months in two modes:for 3, 6and 9 months in two modes:(A). Static regime;(A). Static regime;(B). D(B). Dynamicynamic regime.regime.

(A)(A)STATIC REGIME:STATIC REGIME:--Immersion of 300 cmImmersion of 300 cm33 of SCKof SCK--CEN packing in tritiated water CEN packing in tritiated water (1Ci/l);(1Ci/l);--Decontamination of PtDecontamination of Pt--catalyst and its catalyst and its physicophysico--structural structural characterisation after 3, 6 and 9 months from immersion;characterisation after 3, 6 and 9 months from immersion;--Determination of physical and chemical parameters of process Determination of physical and chemical parameters of process water before and after exposure to water before and after exposure to ββ--tritium radiationtritium radiation..

ENDURANCE TEST IN DYNAMIC REGIMEENDURANCE TEST IN DYNAMIC REGIME

∗∗ SCKSCK--CEN packing will equip isotopic exchange column and it will be dCEN packing will equip isotopic exchange column and it will be daily aily exposed to (1 Ci/l) tritiated water (in closed circuit) and wateexposed to (1 Ci/l) tritiated water (in closed circuit) and water vapour (see figure of r vapour (see figure of experimental installation)experimental installation)∗∗ Experimental conditions: temperature (40Experimental conditions: temperature (4000 C), atmospheric pressure, C), atmospheric pressure, tritiadedtritiadedwater, natural hydrogen( 45water, natural hydrogen( 45--50 50 ppmppm deuterium)deuterium)∗∗ Decontamination of PtDecontamination of Pt--catalyst and its catalyst and its physicophysico--structural characterisation after 3, structural characterisation after 3, 6 and 9 months from immersion.6 and 9 months from immersion.* Evaluation of separation performances after 3, 6 and 9 month o* Evaluation of separation performances after 3, 6 and 9 month of exposure in the f exposure in the following conditions:following conditions:--temperature: 40temperature: 4000 CC--atmospheric pressureatmospheric pressure--flow rates: 5L/min for Hflow rates: 5L/min for H22 and 1 ml/min. for tritiated waterand 1 ml/min. for tritiated water--gas/liquid ratio:3.5; (G=10 mole / mgas/liquid ratio:3.5; (G=10 mole / m22.s).s)--tritium free watertritium free watertritiated hydrogen (.100 tritiated hydrogen (.100 MBqMBq/mole)/mole)

To Stack(G,y0)IomizationChamber

PhaseSplitter 1Condenser 1

Liquid N2

5A Molecular Sieve Trap

To LiquidScintillation Analyse

(V,xc) Oxygen

Catalytic Burner

Condenser 2

PhaseSplitter 3

To LiquidScintillation Analyse

Hydrogen Tank

Saturating Vassel

Saturating Vassel

H2O Tank

HTO Tank

5A Molecular Sieve Trap

Liquid N2

PhaseSplitter 2

H2

HTO Tank

(L,xi)

(L,xD)

Trickle-Bed Reactor

LPCE Columnwith SCK-CEN Packing

Thermostat

Metering Pump

P1

F

F

T1

Layout of endurance test facility of SCKLayout of endurance test facility of SCK--CEN packingCEN packing

EXPERIMENTAL WORKSEXPERIMENTAL WORKS

11. Commissioning of the experimental installation static and . Commissioning of the experimental installation static and dynamic exposuredynamic exposure

2. Exposure of SCK2. Exposure of SCK--CEN packing, continuously for 6.5 months CEN packing, continuously for 6.5 months at tritiated 1 Ci / L water in static and dynamic regimeat tritiated 1 Ci / L water in static and dynamic regime

3. Investigation of physico3. Investigation of physico--structural parameters of MO 1254 structural parameters of MO 1254 catalyst from SCK packing, before and after 3 months catalyst from SCK packing, before and after 3 months exposure.exposure.

4. Investigation of process water quality.4. Investigation of process water quality.

5. Evaluation of separation performances of SCK5. Evaluation of separation performances of SCK--CEN packing CEN packing before and after 6.5 months exposure at before and after 6.5 months exposure at ββ--tritium radiation.tritium radiation.

6. Continuously exposure and endurance test for 6 months is 6. Continuously exposure and endurance test for 6 months is ongoingongoing..

Table 2. Physico-structural parameters of MO 1254 catalyst before and after 3 months exposure at β-tritium radiation

Value No Property Analysis test method

Before exposure After exposure 1 Platinum Content, (%wt) INCERP METHOD 0.916 0.914 2 Macropore Volume (cm3/g) ASTMD 4284-92 0.1467 0.1397 3 Micropore Volume, (cm3/g) ASTMD 4222-91 0.1005 0.0413 4 Pore Average Radius (A) 42.15 57.76 5 Specific Area (m2/g)

ASTMD 3663-

92+ ASTMD 4365-95 117.3235 98.677

Adsorbed H2 Volume (cm3/g cat)

0.58 0.47

H/Pt Dispersion (atom H/atom Pt)

1.06 0.89

6 Metalic Active Surface and Platinum Particle Size: ASTMD 3908-88 (93)

Platinum Active Surface, (m2 /g Pt Surface

290 274

7 Platinum Particle Size Pt, Å 8.1 9.6 8 Distribution Calculation by

Pore Radius 0-10 Å 10-15 Å 15-20 Å 20-25 Å 25-50 Å 50-100 Å 100-150 Å 150-200 Å 200-300 Å 300-600 Å 600-1000 Å 1000-5000 Å 5000-10000 Å 10000-75000 Å

ASTMD 4641-93 14.27 6.32 2.60 1.64 13.82 1.21 0.50 0.15 0.16 7.78 5.23 20.36 9.16 16.8

11.13 5.18 2.43 1.00 2.37 0.43 0.17 0.05 0.06 9.90 6.98 27.74 12.27 20.29

COMMENTS OF RESULTS (I)COMMENTS OF RESULTS (I)

••The fresh catalyst has a good porosity and PtThe fresh catalyst has a good porosity and Pt--particle size, a high particle size, a high metallic area and platinum dispersion ,comparable with conventiometallic area and platinum dispersion ,comparable with conventional nal catalysts. catalysts.

••In comparison with initial values for fresh catalyst the physicIn comparison with initial values for fresh catalyst the physic--structural parameters for the catalyst 3 months exposed at tritistructural parameters for the catalyst 3 months exposed at tritiated ated water are slight lower but no significant modifications. Metal water are slight lower but no significant modifications. Metal content, content, macropores volume, platinum particle sizes are very near macropores volume, platinum particle sizes are very near

••The micropore volume, metallic active area and surface area, sliThe micropore volume, metallic active area and surface area, slightly ghtly decrease after exposure at tritiated water.decrease after exposure at tritiated water.

••Distribution calculation by pore radius confirms this trend and Distribution calculation by pore radius confirms this trend and the the phenomenon is probably due to blocking of micropores during isotphenomenon is probably due to blocking of micropores during isotopic opic exchange process.exchange process.

Table 3. Quality of fresh water and after continuous contact with SCK – CEN packing Type of sample pH Conducti-

vity μS/ cm

KMnO4 demand,

mg/l

Total Fe

mg/ l

F-, mg/ l

Cl-, mg/ l

Fresh water 6,47 1,72 2,2 < 0,01 < 0,02 < 0,1 After 2 weeks 6,16 54,4 26,5 < 0,01 0,31 14,5 After 3 weeks 6,2 36,4 11,6 < 0,01 0,29 8,3 After 4 weeks 6,08 24,59 4,7 0,03 0,27 3,6 After 5 weeks 6,0 18,69 3,8 < 0,01 < 0,18 1,3 After 6 weeks 6,24 6,94 4,3 < 0,01 < 0,11 0,23 After 7 weeks 5,95 9,08 4,8 < 0,01 < 0,05 0,20 After 8 weeks 6,15 8,16 6,3 < 0,01 <0,02 0,18 After 9 weeks 5,97 9,15 4,1 < 0,01 < 0,02 0,14 After 10 weeks 6,3 8,35 3,88 < 0,01 < 0,02 0,1 After 11 weeks 6,4 7,99 4,1 < 0,01 < 0,02 < 0,1 After 1 month 6,35 8,51 5,6 < 0,01 < 0,02 < 0,1 After 2 months 6.40 7.79 4.4 < 0,01 < 0,02 < 0,1 After 3 months 6.30 8.02 3.96 < 0,01 < 0,02 < 0,1 After 4 months 6..4 8.13 4.98 < 0,01 < 0,02 < 0.1 After 6.5 months 6.38 7.97 4.5 < 0,01 < 0,02 < 0.1

COMMENTS OF RESULTS (II)COMMENTS OF RESULTS (II)

•• The conductivity, pH, KMnO4 demand, chlorine, fluorine and totaThe conductivity, pH, KMnO4 demand, chlorine, fluorine and total iron content of water l iron content of water have been measured by conventional chemical methods, before and have been measured by conventional chemical methods, before and periodically after periodically after starting endurance teststarting endurance test

•• At beginning of endurance test all parameters of process water At beginning of endurance test all parameters of process water are much higher in are much higher in comparison to fresh water (distillated water) but after repeatedcomparison to fresh water (distillated water) but after repeated washings of SCK packing , washings of SCK packing , the values for all parameters significantly decrease. the values for all parameters significantly decrease.

•• Some amounts of chlorine and fluorine have been identified in pSome amounts of chlorine and fluorine have been identified in process water but on time rocess water but on time the content continuously decrease till reach the initial value fthe content continuously decrease till reach the initial value from fresh water. Their rom fresh water. Their presence could be due to of some chlorine and fluorine traces adpresence could be due to of some chlorine and fluorine traces adsorbed during preparation sorbed during preparation of the catalyst or during chemical treatment of stainless steel of the catalyst or during chemical treatment of stainless steel spirals. Their presence in spirals. Their presence in larger amounts could reduce the catalytic activity. larger amounts could reduce the catalytic activity.

•• Iron and copper have not been identified in fresh or process wIron and copper have not been identified in fresh or process water.ater.

•• The conductivity and oxidability of process water is also increThe conductivity and oxidability of process water is also increased at beginning of ased at beginning of endurance test and then gradually decrease without to reach the endurance test and then gradually decrease without to reach the value of fresh water. The value of fresh water. The presence of other cations and anions has to be investigated.presence of other cations and anions has to be investigated.

•• After a month of continuously testings, all physicoAfter a month of continuously testings, all physico--chemical parameters of process water chemical parameters of process water reach the initial values of fresh waterreach the initial values of fresh water

Table 4. Performances of SCK-CEN Packings

Catalyst Sample G/L H (OG) cm

HETPcm

K (mole/ m3*s)

Old SCKPacking

3.51 9.0 11.4 123

New SCK Packing

3.84 9.4 11.6 118

Performances of SCK-CEN packing before and after exposure to tritiated water in dynamic regime

Fresh Packing DATA G (l/h) L ml/min YINTRARE

(mCi/l H2O)YIESIRE

(mCi/l H2O)XIESIRE

(mCi/l H2O)K

(mol/m3s)HOG (cm)

HETP (cm)

02.07 - 1,40 610 0,09 1290 101,26 11,69 16,56 05.07 - 1,35 583 0,07 1387 111.73 10,6 14,77 06.07 - 1,39 598 0,10 1198 96,86 12,23 17,26 06.07 - 1,38 600 0,08 1525 115,85 10,22 14,38

After 3 months DATA G (l/h) L ml/min YINTRARE

(mCi/l H2O)YIESIRE (mCi/l H2O)

XIESIRE (mCi/l H2O)

K (mol/m3s)

HOG (cm)

HETP (cm)

25.06 300 1,48 580 0,07 1020 94,69 12,51 18,14 26.06 300 1,37 595 0,08 1139 97,18 12,19 17,09 26.06 300 1,34 607 0,063 980 93,09 12,72 17,67 28.06 300 1,39 605 0,075 1187 99,31 11,92 16,83 After 6,5 months DATA G (l/h) L ml/min YINTRARE

(mCi/l H2O)YIESIRE (mCi/l H2O)

XIESIRE (mCi/l H2O)

K (mol/m3s)

HOG (cm)

HETP (cm)

07.10 300 1,55 594 0,01 790 105,15 11,26 16,67 07.10 300 1,4 520 0,01 820 109,90 10,78 15,26 11.10 300 1,3 510 0,01 720 105,58 11,22 15,37 11.10 300 1,4 490 0,005 690 112,03 10,57 14,97 12.10 300 1,59 510 0,01 728 105,95 11,18 16,74 12.10 300 1,5 657 0,009 726 102,07 11,60 16,93

COMMENTS RESULTS (III)COMMENTS RESULTS (III)

•• Evaluation of separation performances for SCKEvaluation of separation performances for SCK--CEN packing has confirmed the CEN packing has confirmed the good performances reported by SCKgood performances reported by SCK--CEN in previous reports. The difference CEN in previous reports. The difference between the separation performances of SCK packing determined bybetween the separation performances of SCK packing determined by ICIT and SCKICIT and SCK--CEN is of 10%. This difference is due to isotopic mass balance eCEN is of 10%. This difference is due to isotopic mass balance errors.rrors.

•• After 6,5 months endurance test performed in above mentioned coAfter 6,5 months endurance test performed in above mentioned conditions of nditions of continuously exposure to 1Ci/l tritiated water, in dynamic regimcontinuously exposure to 1Ci/l tritiated water, in dynamic regime, no significant e, no significant modifications of separation performances have been observed. modifications of separation performances have been observed.

•• The slight modification of some physicoThe slight modification of some physico--structural parameters of catalyst, and of the structural parameters of catalyst, and of the quality of water during the endurance test, in above mentioned cquality of water during the endurance test, in above mentioned conditions, don't onditions, don't significantly affect the performances of SCKsignificantly affect the performances of SCK--CEN packing. This behavior of SCKCEN packing. This behavior of SCK--CEN packing has to be confirmed during the next step of endurancCEN packing has to be confirmed during the next step of endurance test, planned for e test, planned for others 3 months. others 3 months.

CONCLUSIONSCONCLUSIONS

•• The influence of The influence of ββ-- tritium radiation and of impurities on MO 1254 catalyst and on tritium radiation and of impurities on MO 1254 catalyst and on the the separation performances of SCKseparation performances of SCK--CEN packing in detritiation water process by isotopic CEN packing in detritiation water process by isotopic exchange in liquid phase has been investigated in dynamic and sexchange in liquid phase has been investigated in dynamic and static regime, for 6.5 tatic regime, for 6.5 months.months.

•• The initial separation performances of SCKThe initial separation performances of SCK--CEN packing remain almost constant after CEN packing remain almost constant after 6.5 months exposure to 1Ci/l tritiated water in dynamic and stat6.5 months exposure to 1Ci/l tritiated water in dynamic and static regimeic regime

•• The physicThe physic--structural parameters of MO 1254 catalyst from composition of SCstructural parameters of MO 1254 catalyst from composition of SCKK--CEN CEN catalyst are comparable to conventional Ptcatalyst are comparable to conventional Pt--catalyst. After 3 months continuously exposure catalyst. After 3 months continuously exposure to 1Ci/l tritiated water, no significant modifications of catalyto 1Ci/l tritiated water, no significant modifications of catalyst' physicst' physic--structural structural parameters have been observed. Only micropore volume, metallic aparameters have been observed. Only micropore volume, metallic active area and surface ctive area and surface area, tend slightly to decrease after exposure.area, tend slightly to decrease after exposure.

•• Some amounts of chlorine and fluorine have been identified in Some amounts of chlorine and fluorine have been identified in process water but on process water but on time, their content continuously decrease' till reach the initiatime, their content continuously decrease' till reach the initial value of feeding water. On l value of feeding water. On the other hand, at the beginning of endurance test, the conductithe other hand, at the beginning of endurance test, the conductivity and KMnO4 demand vity and KMnO4 demand are also increased and gradually decrease without to reach the vare also increased and gradually decrease without to reach the value of fresh water.alue of fresh water.

•• This behavior of SCKThis behavior of SCK--CEN packing has to be confirmed during the next steps of CEN packing has to be confirmed during the next steps of endurance test, planned for others 3 months.endurance test, planned for others 3 months.

PERMEABILITY OF TRITIUM INTO PERMEABILITY OF TRITIUM INTO DIFFERENT MATERIALS AS A FUNCTION DIFFERENT MATERIALS AS A FUNCTION OF PARTIAL PRESSURE, TEMPERATURE OF PARTIAL PRESSURE, TEMPERATURE

AND CONCENTRATIONAND CONCENTRATIONNational Institute for Cryogenics and Isotope Technologies,National Institute for Cryogenics and Isotope Technologies,

Rm. ValceaRm. Valcea

S. Brad, I. S. Brad, I. StefanescuStefanescu, L. Stefan, M. , L. Stefan, M. ZamfiracheZamfirache, A. , A. BorneaBornea, A. Lazar,, A. Lazar,F. F. VasutVasut, N. , N. BidicaBidica

Association EURATOM - MEdC

Collaboration with:Association EURATOM - FZK, Karlsruhe, Germany

Tritium permeation into various materials as a Tritium permeation into various materials as a function of gas composition, partial pressure and function of gas composition, partial pressure and temperature is relevant to:temperature is relevant to:

design and construction of fusion reactor design and construction of fusion reactor equipmentequipmenttritium storagetritium storage

Need for a program to investigate tritium Need for a program to investigate tritium permeation:permeation:Exposure to gaseous tritium of reactor equipmentExposure to gaseous tritium of reactor equipmentChanges of material properties as a result of Changes of material properties as a result of tritium permeationtritium permeationIdentification of new techniques for tritium Identification of new techniques for tritium decontaminationdecontamination

Pilot Plant for Tritium Separation(outside view)

Industrial plants who use cryogenic process like plants for liquIndustrial plants who use cryogenic process like plants for liquid hydrogen id hydrogen distillation impose to use material with high tenacity in order distillation impose to use material with high tenacity in order to assures safety in to assures safety in working. In order to verify materials and equipment that work atworking. In order to verify materials and equipment that work at cryogenic cryogenic temperatures, it was necessary to realize a testing stand to dettemperatures, it was necessary to realize a testing stand to determine fracture ermine fracture energy of different materials at cryogenic levels temperature.energy of different materials at cryogenic levels temperature.The experimental setThe experimental set--up developed allows to verify fracture energy for stainless up developed allows to verify fracture energy for stainless steels which, after that, were used in the construction of equipsteels which, after that, were used in the construction of equipment ment from "Experimental Plant for Tritium and Deuterium Separation" ffrom "Experimental Plant for Tritium and Deuterium Separation" from ICIT rom ICIT Rm.ValceaRm.Valcea. .

Toughness stand with specific polystyrene foam like a thermal Toughness stand with specific polystyrene foam like a thermal protection envelope.protection envelope.

The main element of the older stand was a Dewar recipient The main element of the older stand was a Dewar recipient with liquid hydrogen witch assure the temperatures level of 20 Kwith liquid hydrogen witch assure the temperatures level of 20 Kpermanently, connected with a permanently, connected with a cryogeneratorcryogenerator. . Constructively, the setConstructively, the set--up was realized assemblingup was realized assemblingthree insulated components: liquid hydrogen storage vessel of 0,three insulated components: liquid hydrogen storage vessel of 0,7 l 7 l capacity, the vacuum box and the insulation screen with liquid capacity, the vacuum box and the insulation screen with liquid nitrogen. More than that, in order to decrease the evaporation rnitrogen. More than that, in order to decrease the evaporation rate, ate, between the compartments where placed radiation screen made it between the compartments where placed radiation screen made it from thin copper plate. During the testing procedure, the hydrogfrom thin copper plate. During the testing procedure, the hydrogen en vapors and the environment are separated by helium injection in vapors and the environment are separated by helium injection in order to eliminate the explosionorder to eliminate the explosion dangers. dangers.

Experimental Experimental stand stand

( the old version )( the old version )

STAND MODIFICATIONSTAND MODIFICATION

a)a) b)b)The experimental stand (the new version) The experimental stand (the new version) a) a) –– cryogenic liquid transfer line (between Coldcryogenic liquid transfer line (between Cold--Box and Box and CharpyCharpy device)device)b) b) –– acquisition system for temperature and toughness valuesacquisition system for temperature and toughness valuesc) c) -- ccryogeneratorryogenerator type PPHtype PPHd) d) -- Charpy F040/S testing machineCharpy F040/S testing machine

c)c) d)d)

102

3

1

4

5

7

8 9

6

Inside of the ColdInside of the Cold--Box we design a cryogenic liquid holder in order to accumulate aBox we design a cryogenic liquid holder in order to accumulate a holdhold--up up enough for several resilience tests. The liquid hydrogen cryogeenough for several resilience tests. The liquid hydrogen cryogenerator is a Phillips machine nerator is a Phillips machine type A20 which can make two energy temperature levels at 80K andtype A20 which can make two energy temperature levels at 80K and 20 K. The 20 K. The coldcold escapeescaperate rate waswas calculatedcalculated andand therethere are, for are, for liquidliquid hydrogenhydrogen, , betweenbetween 3W 3W toto 5W 5W dependingdepending thethetemperaturetemperature of of thethe PPH PPH coolingcooling waterwater. For . For thethe calculetedcalculeted valuevalue of of thethe warmingwarming amountamountexchangeexchange betweenbetween twotwo surfacessurfaces, A1 , A1 coldcold surfacesurface andand A2 A2 thethe warmwarm surfacesurface whichwhich surrondsurrond thethefirstfirst oneone, , wewe takentaken intointo accountaccount thethe valuevalue of of thethe freefree wayway of of particparticaale 1 le 1 andand thethe distancedistancebetweenbetween coldcold andand warmwarm surfacessurfaces, d., d.

The main elements which compose the experimental stand are like The main elements which compose the experimental stand are like in the following picture:in the following picture:1.1. ColdCold--box box –– inside is the cryostat for the cryogenic liquidinside is the cryostat for the cryogenic liquid2.2. Liquid hydrogenLiquid hydrogen cryogenerator type PPHcryogenerator type PPH3.3. Cryogenic liquid transfer line (between PPH and ColdCryogenic liquid transfer line (between PPH and Cold--Box)Box)4.4. Cryogenic liquid transfer line (between ColdCryogenic liquid transfer line (between Cold--Box and Box and CharpyCharpy device) device) 5.5. Cryogenic valveCryogenic valve6.6. Resilience testing machineResilience testing machine7.7. Temperature A/D aquisition system Temperature A/D aquisition system 8.8. Toughness A/D acquisition systemToughness A/D acquisition system9.9. Process computerProcess computer10.10. Polystyrene jacketPolystyrene jacket

Internal pipe Internal pipe –– liquid hydrogen liquid hydrogen -- φφ25mm 25mm External pipe External pipe –– vacuumm jacket vacuumm jacket -- φφ112mm112mm

Cryogenic liquid transfer line (between ColdCryogenic liquid transfer line (between Cold--Box andBox andCharpyCharpy device) was constructed by three SS W1.4541 device) was constructed by three SS W1.4541 pipes with the same dimension flanged together. The pipes with the same dimension flanged together. The vacuum sealing system is with O rings pressed vacuum sealing system is with O rings pressed between flanges.This system has a great axial between flanges.This system has a great axial mobility in order to weld or flange the internal mobility in order to weld or flange the internal transfer lines transfer lines system. system. The most important part of the The most important part of the

experimental stand for material toughness in a experimental stand for material toughness in a large range of temperatures is the polystyrene large range of temperatures is the polystyrene jacket of the samples. Transportation of liquid jacket of the samples. Transportation of liquid hydrogen in the sample zone is made trough a hydrogen in the sample zone is made trough a capillary pipe transfer line into the jacket. The capillary pipe transfer line into the jacket. The jacket is made from a plastic material, in our case jacket is made from a plastic material, in our case polysterene foam, with enough internal space in polysterene foam, with enough internal space in order to immerse the sample in the liquid order to immerse the sample in the liquid hydrogen. hydrogen. In In thisthis wayway wewe eliminateeliminate somesomeuncontrolleduncontrolled factorsfactors::

•• thethe explosion explosion factorfactor whowho cancan appearappear atat thethependulumpendulum andand samplesample impact;impact;

•• maintainedmaintained andand controlledcontrolled thethe break break samplesampletemperaturetemperature;;

•• increasingincreasing thethe temperaturetemperature range for range for differentdifferent type type ofof materialsmaterials. . The temperature of the sample is measured with a The temperature of the sample is measured with a thermocouple type E ( or other temperature thermocouple type E ( or other temperature sensors ) introduct in the body of the sample. In sensors ) introduct in the body of the sample. In the final calculus, the breaking energy is corected the final calculus, the breaking energy is corected with a factor induce by the drilled hole and by the with a factor induce by the drilled hole and by the polysterene jacket. polysterene jacket.

Testing zone Testing zone –– with with polysterenepolysterene jacket for samplesjacket for samples

Study of Hydrogen isotopes permeation into various materials as Study of Hydrogen isotopes permeation into various materials as a a function of gas composition, partial pressure and temperaturefunction of gas composition, partial pressure and temperature

The first objective was to design and build an The first objective was to design and build an experimental stand dedicated to the hydrogen isotopes experimental stand dedicated to the hydrogen isotopes permeability investigation for metallic samples, used permeability investigation for metallic samples, used generally as materials for fusion facilities. Few general generally as materials for fusion facilities. Few general requirements has been considered when we started to requirements has been considered when we started to design this new facility. The plate samples were thin discs design this new facility. The plate samples were thin discs with dimension between 20 and 25 mm diameter and 0.1with dimension between 20 and 25 mm diameter and 0.1--0.5 mm thickness. The membrane is squeezed by two 0.5 mm thickness. The membrane is squeezed by two cooper gaskets between knifecooper gaskets between knife--edgeedge--sealed vacuum sealed vacuum flanges. The assembly is connected to a vacuum system flanges. The assembly is connected to a vacuum system and before each experiment the stand was pump all by and before each experiment the stand was pump all by several hours. several hours. All the samples was cleaned with sequential All the samples was cleaned with sequential washes of detergent, distilled water, acetone, and distilled washes of detergent, distilled water, acetone, and distilled water again. water again.

For determination of hydrogen and deuterium isotopes For determination of hydrogen and deuterium isotopes permeation through membrane, the stand was connected permeation through membrane, the stand was connected with a gaswith a gas--chromatograph. For aluminium 99.99% purity chromatograph. For aluminium 99.99% purity the results are shown in the following tablethe results are shown in the following table

Do(mDo(m22/s) Ks(mol/m/s) Ks(mol/m33PP1/21/2))

1.1x101.1x10--77 1.9 700 1.9 700 DD22--AlAl

0.5x100.5x10--55 6.9 7706.9 770HH22--AlAl

1.8x101.8x10--55 7.9 7007.9 700HH22--Al Al

T(K)T(K)

Diffusivity Solubility TempDiffusivity Solubility TemperatureeratureMaterialMaterial

Permeation Permeation experimentalexperimental standstandTable 1Table 1

The measured permeability of HThe measured permeability of H22and Dand D2 2 through materials tested, through materials tested, was quantified and agreed well was quantified and agreed well with previously reported valueswith previously reported values(P=D*Ks).(P=D*Ks).

For tritium permeation the experiments was performed at same conFor tritium permeation the experiments was performed at same concentration of tritium in a centration of tritium in a HT gas. The permeation tests were made at IFIN HT gas. The permeation tests were made at IFIN BucurestiBucuresti for radioactive protection rules for radioactive protection rules reasons, inside of a special glovereasons, inside of a special glove--box, at different tritium concentration values. box, at different tritium concentration values. The variation of the concentration of tritium and of course of tThe variation of the concentration of tritium and of course of the partial pressures was done in he partial pressures was done in a decreasing mode by adding hydrogen gas, in the hydrogen/tritiua decreasing mode by adding hydrogen gas, in the hydrogen/tritium stocking vessel. The m stocking vessel. The program of investigation is shown in the following table. The voprogram of investigation is shown in the following table. The volume of HT gas for each sample lume of HT gas for each sample was 140mL with a total concentration 585, 43 was 140mL with a total concentration 585, 43 µµCi/mLCi/mL. The time period for each test was set at . The time period for each test was set at 100h, and after that, the permeated gas was burned to water in a100h, and after that, the permeated gas was burned to water in a catalyst burner system. The catalyst burner system. The volume of tritiated water, measured by LSC, was 3.5mL. All the svolume of tritiated water, measured by LSC, was 3.5mL. All the samples were protected in amples were protected in order to not have a contact with air because even small amounts order to not have a contact with air because even small amounts of oxygen at the surface can of oxygen at the surface can change the permeation rate. Oxide layers at the surface are usuachange the permeation rate. Oxide layers at the surface are usually used for to reduce lly used for to reduce protiumprotium, deuterium or tritium permeation. Also the permeation of hydrog, deuterium or tritium permeation. Also the permeation of hydrogen through metals is en through metals is influenced by trapping at internal defects.influenced by trapping at internal defects.

Sample Thickness(mm)

Temperature(K)

Pressure before the membrane(Pa)

Total activity(on the burned water)

(Bq)

Al 99.99% 0.25 500K 1.9x105 425.912

Al 99.99% 0.13 500K 1.9x105 486.817

Al 99.99% 0.13 500K 2.2x105 498.124

Al 99.99% 0.13 550K 1.9x105 521.567

Table 2Table 2

The permeation rate was calculated and the value of these is betThe permeation rate was calculated and the value of these is between 4.2ween 4.2÷÷5.6x105.6x1055(mol/msPa(mol/msPa1/21/2) for ) for aluminum membrane. The superior value of this range was achievedaluminum membrane. The superior value of this range was achieved in condition of higher in condition of higher temperature and pressure. In all the experiments the samples wastemperature and pressure. In all the experiments the samples was materials with high purity and materials with high purity and the tests were performed without any contact with atmosphere or the tests were performed without any contact with atmosphere or other impurities for metals. For other impurities for metals. For the the aluminiumaluminium membrane membrane we investigate the possibility of Hydrides formation. The phase we investigate the possibility of Hydrides formation. The phase analysis analysis performed with performed with diffractometerdiffractometer system using Powder Diffraction File database, donsystem using Powder Diffraction File database, don’’t reveal any t reveal any AlAl--H bonds, as could be seen in the bellow diffraction spectra.H bonds, as could be seen in the bellow diffraction spectra.

-- XRD aluminium spectraXRD aluminium spectra

The diffraction spectra is the The diffraction spectra is the same with the ASTM spectra same with the ASTM spectra for aluminium (fcc) for aluminium (fcc) •• AlAl--H bondsH bonds not obtained by not obtained by permeation trough the permeation trough the aluminiumaluminium membranemembrane

The The aluminumaluminum membrane (used at permeation tests) membrane (used at permeation tests) spectra is the same with a spectra of a a normal spectra is the same with a spectra of a a normal aluminumaluminum sample. Permeation test was also made sample. Permeation test was also made for tungsten at 1100K at 2.3xfor tungsten at 1100K at 2.3x101055Pa the permeation rate Pa the permeation rate calculated was P= 7.2x10calculated was P= 7.2x10--77 mol/msPamol/msPa1/21/2 and for nickeland for nickelmembrane at 500K and membrane at 500K and 2.0x2.0x101055Pa the permeation ratePa the permeation ratewas P= 3.1x10was P= 3.1x10--77 mol/msPamol/msPa1/21/2

LSC spectra for Al 99.99%(0.25mm)LSC spectra for Al 99.99%(0.25mm)

For influence oh helium, hydrogen and deuterium on different matFor influence oh helium, hydrogen and deuterium on different materials was chosen two erials was chosen two different types of stainless steel:different types of stainless steel:

Type C%

Si%

Mn%

P%

S%

Co%

Cr%

Mo%

Ni%

V%

Al%

Cu%

N%

Nb%

Ti%

W1.4006(X10Cr13)

0,08-0,12 1 1 0,045 0,030 - 12-14 - - - - - - - -

W1.4404(X2CrNiMo 18 10)

≤0,03 1 2 0,045 0,030 - 16,5-18,5 2-2,5 11,0-14,0 - - - - - -

The samples was cooled down at The samples was cooled down at --20020000C and broken in order to observe the influence on C and broken in order to observe the influence on the toughness. With XRD analysis was determinate the concentratithe toughness. With XRD analysis was determinate the concentration of the Feon of the Feαα% and Fe% and Feγγ%. The %. The other components were induced by a corrosion treatment in diluteother components were induced by a corrosion treatment in diluted solution of d solution of HClHCl (18.3%) or (18.3%) or HNO3(27.7%). The entire components obtain in the materials decreHNO3(27.7%). The entire components obtain in the materials decrease strongly the toughness of the ase strongly the toughness of the steels, with values comprises in 10steels, with values comprises in 10--30%. 30%.

For two samples of W1.4006 was induced a surface mechanical treaFor two samples of W1.4006 was induced a surface mechanical treatment (work tment (work hardening) in order to modify the dislocation concentration. Thehardening) in order to modify the dislocation concentration. The work hardening of a crystalline work hardening of a crystalline material is a complex phenomenon, because the stress necessary tmaterial is a complex phenomenon, because the stress necessary to move a dislocation depends both o move a dislocation depends both on shorton short--range interactions such as the intersection of forest dislocatiorange interactions such as the intersection of forest dislocations, and longns, and long--range interactions range interactions with both near and distant dislocations. For this samples was obwith both near and distant dislocations. For this samples was observed an increase of the toughness served an increase of the toughness and mechanical resistance, in correlation with the increase valuand mechanical resistance, in correlation with the increase value of the dislocation concentration e of the dislocation concentration (dislocations induced by the rolling mechanical process applied (dislocations induced by the rolling mechanical process applied to the samples) to the samples)

Table 3Table 3

Material Temp(K)

Energy (J)

W1.4006(not treated sample) 300 112


W1.4006 (treated sample in acid) 73 80

W1.4006 (treated sample in hydrogen) 73 85

W1.4006 (treated sample in helium) 73 90

W1.4006 (work hardening) 73 95



W1.4404(treated sample in acid) 73 99

W1.4404(treated sample in hydrogen) 73 97

W1.4404(treated sample in helium) 73 98

XRD measurementsXRD measurementsData acquisitions were made with a DRON UM1 Data acquisitions were made with a DRON UM1 diffractometerdiffractometer connected with PC. A horizontal connected with PC. A horizontal powder powder goniometergoniometer in Braggin Bragg--Brentano geometry with Brentano geometry with graphite graphite monochromatormonochromator was used. The incident Cuwas used. The incident Cu--KKαα radiation, radiation, λλ = 1.54178 = 1.54178 ÅÅ was used. The typical was used. The typical experimental conditions were: 2 sec. for each step, experimental conditions were: 2 sec. for each step, range angle 2range angle 2θθ =100=100--1000, step 0.050. The spectra 1000, step 0.050. The spectra obtained in these conditions were used to make obtained in these conditions were used to make qualitative and quantitative phase analysis and to qualitative and quantitative phase analysis and to determine the microstructure parameters by whole determine the microstructure parameters by whole pattern fitting methodpattern fitting method

Type Code Sample description

W1.4006 4006_eta Etalon: Cr (12-14)%, Si (1%), Mn (1%), S (0.03%), P (0.045%), C

(0.08-0.12)%, restul Fe

W1.4006 W1_4006 W1.4006/HCl/30min./470grd/1h

W1.4006 W1_4006a W1.4006/…/790-8200C /30min/HCl

W1.4006 W1_4006b W1.4006/He/740-8200C /30min/HNO3

W1.4006 W_4006c W1.4006/HNO3

W1.4006 W_4006b W1.4006/He/750-8200C /30min.

TypeTypeCodeCode Sample descriptionSample description

W1.4404W1.4404 4404_eta4404_eta Etalon: Cr (12.5Etalon: Cr (12.5--18.5%), Ni (1118.5%), Ni (11--14%), Mo (214%), Mo (2--2.5%),2.5%),

Si (1%), Si (1%), MnMn (2%), S (0.03%), P (2%), S (0.03%), P (0.045%), C under 0.03%, Fe(0.045%), C under 0.03%, Fe

W1.4404W1.4404 W1_4404W1_4404 W1.4404/He/1050 W1.4404/He/1050 00C/1hC/1h

W1.4404W1.4404 W1_4404aW1_4404a W1.4404/H2/30 min/500 W1.4404/H2/30 min/500 00CC /HNO3/HNO3

W1.4404W1.4404 W1_4404bW1_4404b W1.4404/HCl/12 h/H2/30min/470 W1.4404/HCl/12 h/H2/30min/470 00CC

W1.4404W1.4404 W1_4404cW1_4404c W1.4404/1050 grd/5W1.4404/1050 grd/5--10 min/He/470 10 min/He/470 00CC

Table 4Table 4

Table 5.1Table 5.1 Table 5.2Table 5.2

Qualitative phase analysis on W1.4006 and W1.4404 of the presencQualitative phase analysis on W1.4006 and W1.4404 of the presence of Fee of Feαα ((martensitemartensite) and Fe) and Feγγ(austenite) is presented in table 2. The estimated concentration(austenite) is presented in table 2. The estimated concentrations are provided by analysis of figures s are provided by analysis of figures of diffraction pattern. of diffraction pattern.

Samples W1.4006 Concentrations estimated of Feα% and Feγ%

Samples W1.4404 Concentrations estimated of Feα% and Feγ%

4006_eta 0% and 100% 4404_eta 100% and 0%

W1_4006 <1% and >99% W1_4404 <10% and >90%

W1_4006a ~50% and ~50% W1_4404a <1% and >99%

W1_4006b <10% and >90% W1_4404b ~100% and ~0%

W_4006c ~100% and ~0% W1_4404c >99% and <1%

W_4006b ~100% and ~0%

Etalon XRD spectra for W1.4404Etalon XRD spectra for W1.4404

Table 6Table 6

For W1.4404, treated in hydrogen atmosphere, the scanning electrFor W1.4404, treated in hydrogen atmosphere, the scanning electron on micrographymicrography of the of the fracture surface is shown bellow. fracture surface is shown bellow.

SEM for W1.4404SEM for W1.4404

Etalon XRD spectra for W1.4006Etalon XRD spectra for W1.4006

It could be seen the many nuclear cavities from which ridges It could be seen the many nuclear cavities from which ridges emanate. The morphology of internal voids and cracks, in emanate. The morphology of internal voids and cracks, in hydrogen hydrogen embrittledembrittled steels, leaves little doubt that growth steels, leaves little doubt that growth commonly occurs by the development of new surface commonly occurs by the development of new surface progressively at the roots of notches because broad expanses of progressively at the roots of notches because broad expanses of relatively smooth surface are exposed. Fracture studies using relatively smooth surface are exposed. Fracture studies using the scanning electron microscopy seem to place the sites of the scanning electron microscopy seem to place the sites of cavity nucleation too far apart in relation to the height of thecavity nucleation too far apart in relation to the height of theridges of final rupture, as could be seen in the figure. Fracturridges of final rupture, as could be seen in the figure. Fracture e has followed grain boundaries. has followed grain boundaries.

CONCLUSIONSCONCLUSIONS

For the For the Hydrogen isotopes permeation into various materials as a functioHydrogen isotopes permeation into various materials as a function of gas composition, n of gas composition, partial pressure and temperature we can conclude:partial pressure and temperature we can conclude:

••Increasing values for HIncreasing values for H22 and Dand D22 permeation was observed at the increasing of the pressure permeation was observed at the increasing of the pressure and of the temperatureand of the temperature••Permeability of HPermeability of H22 and Dand D22 through materials tested was quantified and agreed well with through materials tested was quantified and agreed well with previously reported values previously reported values ••Increasing values for HIncreasing values for H22 and Dand D22 permeation was observed at a low increasing of the pressurepermeation was observed at a low increasing of the pressure••Increasing values for HIncreasing values for H22 and Dand D22 permeation was observed at a low increasing of the permeation was observed at a low increasing of the temperaturetemperature••The permeation experiments show an increase of the tritium permeThe permeation experiments show an increase of the tritium permeation rate at a slightly ation rate at a slightly increasing of temperature and pressure. increasing of temperature and pressure. ••Oxide layers at the surface reduce Oxide layers at the surface reduce protiumprotium, deuterium or tritium permeation. , deuterium or tritium permeation. ••Permeation of hydrogen trough metals is influenced by trapping aPermeation of hydrogen trough metals is influenced by trapping at internal defects. t internal defects. ••Superior value of permeation rate will be achieved in condition Superior value of permeation rate will be achieved in condition of higher temperature and of higher temperature and pressure. pressure. ••For aluminum For aluminum we determine the impossibility of Hydrides formation.we determine the impossibility of Hydrides formation.

For toughness stand with specific polystyrene foam like a thermaFor toughness stand with specific polystyrene foam like a thermal protection envelope we l protection envelope we can conclude:can conclude:

•• With the jacket used for each breaking sample, we can control wiWith the jacket used for each breaking sample, we can control with a good accuracy the th a good accuracy the value of the temperature and obtain value for the toughness morevalue of the temperature and obtain value for the toughness more closer with the realitycloser with the reality•• The new version of breaking testing stand could be also used at The new version of breaking testing stand could be also used at liquid heliumliquid helium,,connect connect a a specializedspecialized liquid heliumliquid helium DewarDewar and modify and modify thethe temperaturetemperature sensorsensor..•• The toughness experimental stand can be use, in this new versionThe toughness experimental stand can be use, in this new version, in a large range of , in a large range of temperature using different types of cryogenic liquids.temperature using different types of cryogenic liquids.•• The accuracy in the measuring techniques of the materials propriThe accuracy in the measuring techniques of the materials proprieties at low eties at low temperatures and cryogenic temperatures increase economical desitemperatures and cryogenic temperatures increase economical design for cryogenic plants, assure gn for cryogenic plants, assure possibilities to choose the right materials at different temperapossibilities to choose the right materials at different temperature; ture; •• Knowing the materials characteristics in the necessary temperatKnowing the materials characteristics in the necessary temperature range decrease the ure range decrease the fabrication costs for cryogenic plants and increase the saftey ifabrication costs for cryogenic plants and increase the saftey in exploatation;n exploatation;•• The mechanical proprieties of the materials decrease for the samThe mechanical proprieties of the materials decrease for the samples treated in ples treated in corrosive and hydrogen, helium atmosphere. Hydrogen and deuteriucorrosive and hydrogen, helium atmosphere. Hydrogen and deuterium can influence the behavior m can influence the behavior of materials significantly of materials significantly •• The role of the hydrogen and deuterium in fracture mechanism is The role of the hydrogen and deuterium in fracture mechanism is that of a perturbation that of a perturbation on the basic strength of the metals.on the basic strength of the metals. However, as dislocations cannot in general cross a grain However, as dislocations cannot in general cross a grain boundary, they will pile up at the boundary until the stress theboundary, they will pile up at the boundary until the stress there is sufficient to generate slip in an re is sufficient to generate slip in an adjacent grain. adjacent grain. •• For the samples with work hardening treatment, the subsequent deFor the samples with work hardening treatment, the subsequent deformation of the formation of the material, dislocation pilematerial, dislocation pile--ups will occur not only at grain boundaries, but at other obstacups will occur not only at grain boundaries, but at other obstacles les formed during the deformation, e.g. sessile dislocations such asformed during the deformation, e.g. sessile dislocations such as the the LomerLomer--Cottrell barrier in FCC Cottrell barrier in FCC materials. materials. •• For the influence of hydrogen, helium and internal defects, the For the influence of hydrogen, helium and internal defects, the use bodyuse body--centeredcentered--cubic cubic metals at low temperatures have to be under taken with considerametals at low temperatures have to be under taken with considerable care increasing with any ble care increasing with any other external or internal factors.other external or internal factors.

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