New HYDROGENIUS for 2015 and beyond

Joichi SugimuraKyushu University

January 31, 2014

Kyushu University

Kyushu UniversityKyushu University

1877 Fukuoka Hospital1903 Fukuoka Medical College (of Kyoto Imperial University)1911 Kyushu Imperial College founded - College of Engineering1911 Kyushu Imperial College founded - College of Engineering1947 Name changed to Kyushu University1949 Reorganized under the new School Education Law2005 St t d t It C2005 Started a move to Ito Campus

Number of students about 19,000 (1,700 from overseas)Number of faculty members about 2 200Number of faculty members about 2,200

2

Building Ito campus – hydrogen campus

JR Kyuudaigakkentoshi Station

Humanity depts. (plan)NEXT-FC （2013.5）

I2CNER （2012.11） Science depts. (plan)

INAMORI Frontier Research CenterSolar cells

General Undergraduate Education

Engineering depts.HYDROGENIUS（2007.11）

Dept. of Hydrogen Energy Systems

Hydrogen Station

International Research Center Lens wind turbine

p y g gy y

for Hydrogen Energy

R ti Agriculture depts. (plan)

3

Reservation zone

Center of Excellence in Hydrogen

Education ResearchEducation ResearchThe 21st Century Center of Excellence Program (MEXT)

International Research Center for Hydrogen Energy

KYUSHU UNIVERSITYDepartment of

Hydrogen Energy Systems

HYDROGENIUS

y g gy

KYUSHU UNIVERSITYAIST

FUKUOKA PREFECTURE

Systems Graduate School,

Kyushu Univ.I2CNER

NEXT-FCFukuoka Strategy Conference

for Hydrogen Energy

FUKUOKA PREFECTURE Fukuoka Personnel

Training Centerfor Hydrogen Energy

NEXT-FC

o yd oge e gy

Expositions, Forum & Symposia

Enlightenment

4

Missions of HYDROGENIUSMissions of HYDROGENIUSin the first stage (2007-2012)

NEDO“Fundamental Research Project on Advanced Hydrogen Science”j y g

to study fundamentals of hydrogen and materials to be used in hydrogen including mechanism of hydrogen embrittlement ,and to provide data necessary for the development of FCVs stationary FC systems andnecessary for the development of FCVs, stationary FC systems and hydrogen infrastructure

to provide principles for design testing and use of materials forto provide principles for design, testing and use of materials for prolonged use in hydrogen

to contribute to revision of regulations and standardization of materials to co t bute to e s o o egu at o s a d sta da d at o o ate a sfor hydrogen systems

Back to Basics

5

Back to Basics

HYDROGENIUS

h h lFatigue and fracture of structural materials

Thermophysical properties

Polymers & elastomers Tribology

H2 H2

6

Hydrogen supply network High pressure天然ガス or LPG

水素

電力

天然ガス or LPG

水素

電力

Hydrogen supply network

Thermophysicalproperties

High pressure hydrogen

電力電力

Compressor

properties

Structural materials

Polymers/elastomers

Storage tanks

materials

TribologyMain body, Pipes, Components, g

Dispenser

gyp ,Piston ring/liners,Seals, Bearings

p

Pressure vessels, Pipes, Valves, Seals

FCVPipes, Valves, Hose Coupler, Seals

7

Tanks, Pipes, Valves, Seals

HYDROGENIUSHYDROGENIUSFriction test under Friction test under highly controlled highly controlled environmentenvironmentHYDROGENIUSHYDROGENIUS

the world unique the world unique research center for research center for hydrogen materials hydrogen materials

40MPa40MPaTribology Tribology TestersTesters

environmentenvironment

Thermophysical Thermophysical 120MPa Fatigue Test Facilities120MPa Fatigue Test Facilities(3 systems)(3 systems)

Our OriginalOur OriginalInstrumentsInstruments

p yp yDatabase of HydrogenDatabase of Hydrogenup to 100MPaup to 100MPa--773K773K

(3 systems)(3 systems)

Compression Compression depression depression

t ft f

U iU i

apparatus for apparatus for elastomerselastomers(95MPa，100℃）

Unique Unique ObservationObservationTechniqueTechniqueCollaboration Collaboration

with with

Fatigue Test under AirFatigue Test under AirPVT measurementPVT measurement（100MPa，500℃）

organizationsorganizations

Fatigue TestFatigue TestFatigue Test Fatigue Test under 1 MPaunder 1 MPaHydrogenHydrogen

Viscosity measurementViscosity measurement（100MPa，500℃）

8

HYDROGENIUS in Phase II (2013-2017)

HYDROGENIUS was reborn in April 2013 as a research center of Kyushu University in collaboration with NEDOcenter of Kyushu University in collaboration with NEDO, AIST and other organizations and industries.

HYDROGENIUS contributes to development of safe and economical hydrogen systems through establishment of d i d l ti th d i i f d t fdesign and evaluation methods, provision of data for standards and regulations, and data for risk assessment.

9

HYDROGENIUS in phase II (2013-2017)HYDROGENIUS in phase II (2013-2017)

NEDONEDO“Research Project for Hydrogen Utilization Technologies”

to explore introduction of various steel materials to reduce cost, and toto explore introduction of various steel materials to reduce cost, and to develop new hydrogen resistant materials

to establish componentsealing and hose materials technologies for high p g g gpressure hydrogen

to establish standard test methods and design principles for high pressure hydrogen

to improve database of hydrogen thermophysical properties for design

to explore safety evaluation methods for hydrogen systems

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Basics to Practice

Research Sections

Universities, Private companies

AIST Research Units

11

Hydrogen Fatigue and Fracture

Leader Prof. Saburo Matsuoka

Fatigue and Fracture Analysis for safe design

Inspection and AnalysisInspection and AnalysisImportant Findings on Hydrogen Embrittlement

of Hydrogen Refueling Stationsafter DemonstrationAccident Analysis

of Hydrogen Refueling Stationsafter DemonstrationAccident Analysis

1. Hydrogen-enhanced localized plasticity2. Frequency effects of crack growth rate3. Influence of Trace Amount of Hydrogen in Austenitic Stainless SteelsAustenitic Stainless Steels

Design book

Technical information for R&DISO t d d SAE t d d

Technical information for R&DISO t d d SAE t d d

12

ISO-standard、SAE-standardISO-standard、SAE-standardIndustries

HHMechanism of Hydrogen Embrittlement：Frequency effect and the Upper bound

Hydrogen Fatigue and Fracture

10-6

10-5

ycle

)

H：0.49ppmH：0.49ppm

H

H HH

H

H H

H

H HH

H

H HJIS-SCM435

10-7

，da

/dN(

m/c

y

H：0.49ppmH：0.49ppm

da

H

HH HH

H

a da

H

HH HH

H

a

Schematic image of the mechanism of effect ofX30

10 9

10-8

k gr

owth

rate

H：0.47ppmH：0.3ppmH：0.47ppmH：0.3ppm

(f 2H ) 0 58 0 49

Hydrogen-charged

(f=20Hz)：0.49→0.24ppm(f=20Hz)：0.53→0.27ppm

(f 2H ) 0 58 0 49

Hydrogen-charged

(f=20Hz)：0.49→0.24ppm(f=20Hz)：0.53→0.27ppm

Schematic image of the mechanism of effect of hydrogen and test frequency on fatigue crack growth.

Hydrogen-charged(0.56ppm)(0.56ppm)

10 10020 30 40 50 60 70809010-10

10-9

Crac

k

(f=0.2Hz)：0.58→0.49ppm(f=2Hz)：0.58→0.49ppm

Uncharged：0.01ppm

(f=0.2Hz)：0.58→0.49ppm(f=2Hz)：0.58→0.49ppm

Uncharged：0.01ppm

mMPa17≅ΔK120MPaH2 Fatigue

Test system

Stress intensity factor range，ΔK(MPa√m)

Uncharged specimen

(0.54ppm)Relationship between crack growth rateand stress intensity factor of SCM435 steel for a high-pressure cylinder. (R = -1)

・Slow stress cycles in H2 environment accelerates crack growth rate

13

Slow stress cycles in H2 environment accelerates crack growth rate.・Acceleration of fatigue crack growth rate shows an upper limit factor of ca. 30.

Basic mechanism ofHydrogen Embrittlement

Data collection of structural materials

Contribution to regulations

Hydrogen Fatigue and Fracture

10-6

10-5

/dN

[m/c

ycle

]

Type 316 (over 12 mass % Ni), 0 % cold rolling115 MPa H2, RTR = 0.1, ΔK = 20 MPa m1/2

Hydrogen Embrittlement structural materials

1

1.2SUS316 (12% Ni)

(115MPa)

φ H2/φ

Air

: Data Base : JRCM : Austenitic stainless steel１)×

: Data Base : JRCM : Austenitic stainless steel１)×

9

10-8

10-7

k gr

owth

rate

, da/

0.4

0.6

0.8

SUS316(82MPa)at

ive

redu

ctio

n of

are

a, φ

SUS316L(78MPa)

SUS310S(94MPa)

<In 115 MPa H2 (5N) >SUS316 ( over 12% Ni )

<In air, f = 20 Hz >SUS316 ( over 12% Ni )

<In 115 MPa H2 (7N) >SUS316 ( over 12% Ni )

10-4 10-3 10-2 10-1 100 10110-9

Frequency, f [Hz]

Cra

ck

Increase in FCG resistance by supersaturated hydrogen Strength data

Fatigue property of SUS316(>12%Ni）120MPaH2 Fatigue

Test system6 8 10 12 14 16 18 200

0.2

(82MPa)

Rel

aNi content (mass ppm)

SUS304(PH2=82MPa)

supersaturated hydrogen Strength data Construction of hydrogen structural materials DS for hydrogen infrastructure

y

Case studies of hydrogen stationsSGP Steel

y g

Hydrogen diffusion coefficient data

35MPa CylindersSCM435 Steel

EBSD像

14

蓄圧器a 蓄圧器b 蓄圧器c 蓄圧器d Discovery of test frequency effect and upper limit in acceleration of fatigue crack growth rate of the

steel SGP with hydrogen

EBSD像

Case study of 35 MPa hydrogen cylinder

Leader Prof. Shin Nishimura

Hydrogen Polymer Material

EmergencyRelease couplingHydrogen

V l

Hydrogen dispenserHose

Vessel Accumulator

Rubber O-ring

Plug of hydrogen Receptacle on Receptacle Plugdispenservehicles Receptacle Plug

15

Sealing high pressure hydrogen gas

Hydrogen Polymer Material

Sealing high pressure hydrogen gasRubber materials for O-ring (Ethylene propylene rubber strengthened by carbon black)

1 h afterDegassing

4 h 8 h 11 h

O-ring (NBR resin)f ℃ l

10mm

after 100MPa, 30℃×25 Cycles

Seal failureSeal failure

BlisterBlister140mm

断面

→ Improvement of performance by changing filler from Carbon black→ Improvement of performance by changing filler from Carbon black

5.5mm

16

Improvement of performance by changing filler from Carbon black to Silica which does not absorb hydrogen

Improvement of performance by changing filler from Carbon black to Silica which does not absorb hydrogen

Development and test methods for rubber materials and polymeric

Hydrogen Polymer Material

m)

1400 Model Compound Fracture Mechanicsli

Development and test methods for rubber materials and polymeric materials for hydrogen gas seal and hose under 82 MPa

O-ring squeeze ratio＝1ーH／d1・・・10～20%Filli ti A ／A 60 80%

Cont

ent

at 1

0 M

Pa(p

pm

EPDM–CB25phr

EPDM–CB50phr

NBR–CB50phr

Blister

NBR–CB25部

U fill d

600

800

1000

1200

1400 Model Compound Data Collection

Defect Origin

M i

Time

Grow of Blister

Grow of Blister

Molecular ChainBlisterCrosslink

Defect

H d1AOR

Filling ratio＝AOR／AG・・・60～80%

Critical Pressure of Blister Fracture, ΠF, MPa

Hyd

roge

n C

No BlisterEPDM–SC60phr

NBR–SC60phrEPDM–WC95Unfilled

EPDMUnfilledNBR

0 2 4 6 8 100

200

400 Matrix Origin

Time AG=H × LLd1:O-ring Diameter，H: Gland hight，L: Gland widthCross section area: AOR:O-ring ，Gland

Development of Material Prototype Evaluation Product Evaluation Material Design Model Compound Data Fracture Modeling Design Guideline

O-rings

m）

Chemical Analyses Properties in Hydrogen Damage/Lifetime Analyses

Hydrogen Content

Solid State NMR Hoses

Product

c )c )

c )

Two types of dissolved hydrogenCB filled EPDM

10MPa, 30℃，24hours

●：Experimental Value−：Calculated Value

n Co

nten

t （m

ass.

pp

Solid State NMR

100℃

80℃ 30℃

Pres

sure

(MPa

)

100

Pressure Cycle Test of O-ring

Product Testing：Collaboration with Hydrogen Testing & Research

178 7 6 5 4 3 2 1 0C h e m ica l sh ift (δ in p p m )

U n e xp o

3 5 H2 3 H

1 4 H1 H

C ru d e N B R

g )b )

f)

a )

e )

g )

d ) h )

c )

5 5 H

Chemical Shift（ppm） Elapsed Time（sec）

Hyd

roge

n

Hyd

roge

n P

10101 100 1000 10000

Cycle Number of Failure

Center

17

Hydrogen Tribology

Leader Prof. Joichi Sugimura

F i ti d l b i ti fFriction, wear and lubrication of materials in hydrogen systems

18

Unique and comprehensive hydrogen tribology researches

Hydrogen Tribology

Surface analysis for investigating mechanisms of processes at tribo-interface

Experimental techniques

q p y g gy

Tribotests under controlled gas trace impurities,

p ocesses at t bo te ace

気体g p ,tribotests in 40 MPa hydrogen, cyclic contact tests, rolling contact fatigue tests, tec.

表面層Tribotests for various materials

○Adsorption, reaction, permeation of hydrogen and 1.0E-08

1.0E-07

1.0E-06

量, m

m^2

/N

0.50.60.70.8

0.91

摩擦係数

30405060708090

損確率

, ％

水素アルゴン空気

固体

表面層

1.0E-06

1.0E-05

1.0E-04

ear r

ate,

mm

3 /Nm

1.0x10-4

1.0x10-5

1.0x10-6

PTFE

PTFE + Graphite

p y gtrace impurities○Changes in properties of surface and subsurface○Transfer and wear of materials

1.0E-10

1.0E-09

0.1 1 10 100水分濃度, ppm

比摩耗

00.1

0.20.30.4 摩

ピン＋ディスク

摩擦係数58

101520

10 100 1000 10000 100000

累積破損

寿命, ×104サイクル

Rolling contact fatigue life ofVariation of friction and wear of Friction and wear of PTFE

1.0E-08

1.0E-07

0.1 0.2 0.3 0.4

Spec

ific

we

Coefficient of friction

1.0x10-8

1.0x10-7

PTFE + Bronzein Hydrogen

PTFE + Bronzein Helium

Rolling contact fatigue life of 52100 steel （SUJ2, PAO10, 4.8GPa, 90℃, Λ=1.69）

Variation of friction and wear of 316L steel in hydrogen with trace of water （10N, 6.3mm/s）

Friction and wear of PTFE composites slid against 316L steel in 40MPa hydrogen●and helium●

19

Contribution to industries with tribology data and design principles

Friction and wear of sealing materials for high pressure hydrogen

Friction and wear properties of polymeric materials for dynamic sealsp y y

Contact and friction behaviors of elastomeric materials for static seals

O ring

Pressure

Hydrogen Thermo-physical Property

Leader Prof. Yasuyuki Takata

Start of measurement of hydrogen thermo-physical property for low temperature and low pressure by NASA for rocket fuel.p p yHydrogen property at high temperature and high pressure is necessary for design of fuel cell systems.

Accurate fueling system

Rapid fueling systemfueling system

Database of thermophysical properties of hydrogenDatabase of thermophysical properties of hydrogen

21

Database of thermophysical properties of hydrogenDatabase of thermophysical properties of hydrogen

PVT(E ti f St t )PVT(E ti f St t ) Th l C d ti itTh l C d ti it

Thermophysical properties necessary in design

H Generator

PVT(Equation of State)PVT(Equation of State) Thermal ConductivityThermal Conductivity

Heat Heat TransferTransfer

DewDewSpecific Specific

H tH tViscosityViscosityH2 Generator Dew Dew

PointPointHeatHeat

yy

Precooler

Compressor Accumulator －60℃

Sound VelocitySound Velocity• Measurement of refueling mass flow rate by PVT data

Dispenser

Sound VelocitySound Velocity

• Estimation of H2 leak rate from a crack・・・・・Sound velocity

• Estimation of pressure drop・・・・・・・Viscosity

70MPa H2 Tank• H2 Purity monitor・・・・・・・Dew point

• Estimation of H2 leak rate from a crack・・・・・Sound velocity

f f

22

Thermophysical property data for hydrogen is a basis of hydrogen society and therefore, the database including accurate PVT, thermal conductivity, viscosity, sound velocity and specific heat is essential. 22

Development of apparauts for thermophysical property measurement Outcome 2006-2012

Hydrogen Thermo-physical Property

measurementMeasurements of H2 thermophysical properties

○PVT data and virial Equation Of State up to 100MPa, 500℃○Measurement and prediction equation for viscosity up to 100MPa and 500℃220 - 350 K

Isochoric PVT apparatus

○Measurement and prediction equation for thermal conductivity up to 100MPa and 500℃○Development of H2 thermophysical property database

C ill i t

1 5 10 50 100-0.4-0.2

00.20.4

220 350 K

300 K250 K

0.20.4

350 - 400 K

393 15 K

353.15 K

OS)

/ ρ v

irial

EO

S

Isochoric PVT apparatus(∼100MPa, 500°C)

Capillary viscometer(∼100MPa, 250°C)

0 4-0.2

00.20.4

400 - 500 K

433.15 K

473.15 K

1 5 10 50 100-0.4-0.2

0 393.15 K

100(

ρ - ρ

viria

l EO

PVT data and EOS

1 5 10 50 100-0.4

P , MPa

Burnett type PVT(∼100MPa 200°C)

Thermal conductivity(∼100MPa 500°C) 0 25

0.30

0.35

0.40

0.45

熱伝導率

[W/(m

·K)]

ノーマル水素

300°C

200°C

100°C150°C

50°C0°C

-50°C

400°C

500°C

14

16

18

20

sity

, η μ

Pa·s

HYDROGEN ExperimentalT:296.15K

Nabizadeh (1999)T:298.15K

Michels (1953) Gracki (1969) Barua (1964) Golubev (1953) Kuss(1952)

T:299.15K Rudenko (1968) Present correlation

FPROP

Michels

(195

3)

(∼100MPa, 200 C) (∼100MPa, 500 C)

0 20 40 60 80 1000.10

0.15

0.20

0.25熱

圧力 [MPa]

-100°C

Roder's correlation

Vi itHighly ingenious

0 50 100 150 2008

10

12

Pressure, P MPa

Vis

cos

REFPR

McCarty (1972)

Diler (1965) Hanley (1972)

23

Viscosityg y g

measurement apparatus Contribution to industry by supplying a reliable database

Thermal conductivity

Hydrogen Safety

Leader Prof. Nobuhiro Kuriyama

Hydrogen safety analysis

Failure in systems and componentsFailure in systems and componentsHuman error

Analysis of “Near miss incidents reports”Analysis of Near miss incidents reportsRisk assessment - from high pressure research facilities to practical systems

24

to practical systems

Cooperation with Industry and Government

FundamentalsN M th d

Hydrogen Energy Test ＆Research Center (HyTReC)

Education Programfor Engineers and Students

New MethodsMaterials Data etc.

Research Center (HyTReC)

H d S tHydrogen SystemSafe, Reliable, and Low Cost

Policy Making Development of

International Forum

Policy MakingCodes & Standards

Development ofHydrogen Systems

METI, NEDO, KHK INDUSTRIES

25

Local Governments(Fukuoka Pref. etc.)

Automobile, EnergyEngineering etc.

Thank you for your attention !