Engineering the Quantum Mechanics of Cold Hydrogen

H H Y drogen P roperties for E nergy R esearch Jacob Leachman, Associate Professor School of Mechanical & Materials Engineering [email protected] (509)335-7711 http://hydrogen.wsu.edu @hydrogenprof Jacob Leachman • School of Mechanical and Materials Engineering HYPER Jacob Leachman • School of Mechanical and Materials Engineering HYPER 2 1 Meet H ydrogen the #youniversal energy carrier. 1.00794 In this talk: 1) Foundational science enabling 2) Engineering applications with -- Ortho-parahydrogen manipulation -- Hydrogen quantum tunneling 3) Resulting in a sustaining pipeline to space Kardeshev Level 3: Galactic energy

Kardeshev Level 2: Solar system energy Kardeshev Level 1: Sustainable planetary energy Kardeshev Level 0: Jacob Leachman • School of Mechanical and Materials Engineering HYPER 3 Fossil & Organic energy 1. Foundational Science

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 4 Foundations: The story of how it all began (UIdaho 2005)

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 5 Foundations: The Hydrogen Family Isotopic Hydrogen Non-isotopic Allotropes (spin – isomers) Molecules Atoms Molecules

Orthohydrogen Parahydrogen Hydrogen Protium Hydrogen-Deuteride

Paradeuterium Orthodeuterium Deuterium Deuterium Hydrogen-Tritide

Orthotritium Paratritium Tritium Tritium Deuterium-Tritide

= Nuclear spin = Proton = Neutron = Electron and = Covalent orbit bond

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 6 Foundations: The Physics of Nuclear-Spin Isomers In 1932, Werner Heisenberg won the Nobel Prize:

“for the creation of quantum mechanics, the application of which has, inter alia, led to the discovery of the allotropic forms of hydrogen.”1 Partition function:

n −EvJ / kT Normal Zn=+ i(21 J) E vJ e Hydrogen vJ 0 3:1 Equilibrium ratio: Equilibrium Cp : 2 Z ZZ −2 5 Orthohydrogen Parahydrogen ortho,0 0 21 K = CPB= R −( k T ) + op Z ZZ 2 para,0 00 0 All other ortho-para composition Cp : 2 2 ZZ ZZ −2 5 0 para,2 para ,1 ortho,2 ortho ,1 CP, mix= R y para − + y ortho −( k B T ) + ZZZZ  2 para,0 para ,0 ortho ,0 ortho ,0 1Nobelprize.org accessed 2010 Jacob Leachman • School of Mechanical and Materials Engineering HYPER 7 Foundations: Ortho-para effects on properties • Ortho-para spin conversion is not spontaneous and can be driven by catalysis.

Latent heat of vaporization

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 8 Foundations: Significance of ortho-para manipulation

“Partial ortho-para conversion.. Offers the greatest opportunity for reduced liquefaction power consumption.” ~C. Baker 1979

“Because of the entropy difference between ortho- and parahydrogen, it is tempting to think of some external force which could change the equilibrium concentration at some temperature. Practical levels of electric field gradients or magnetic fields would have only a minor effect on the equilibrium concentration, though further studies may be useful.” ~ Ray Radebaugh 1982

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 9 Foundations: Need for accurate Equations Of State (EOS)

• Forms the foundations for engineering design and custody exchange • Old formulation (pre 2007) did not account for ortho-para differences • Upper limit of 400 K • 0.2% density uncertainty • Unphysical behavior • Worst EOS in NIST databank

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 10 Foundations: Fitting Fundamental Equations of State

• Explicit in reduced Helmholtz Free Energy and partitioned into ideal and real- fluid contributions – all other properties are fast derivatives away.

Ideal-Fluid Real-Fluid 0 r ( ,,, ) =+ (  ) (   ) x y r di t i d i t i p i ( , ) =NNii   +   exp( −  ) + i==1 i x z 22 NDdtii exp   − +   −  0  i i( i) i( i )  ( , ) = ln  − ln  + iy= a  ik + a ln 1− exp − b   k  k  ( k ) • A non-linear Levenberg-Marquardt algorithm optimizes the empirical terms.

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 11 Foundations: Real-fluid ortho- Leachman et al. Younglove (1982) para property differences

• O-P Densities diverge below 60 K. • Vapor pressures up to <5 %. • Real fluid caloric properties up to <3 %. • Incomplete data sets between fluids. • Needed a way to scale between ortho and parahydrogen to make separate but consistent equations of state.

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 12 Foundations: Scaling the Quantum Hydrogen

In 1929, Louis de Broglie won the Nobel Prize: “for his discovery of the wave nature of electrons.”1

6.00E-10

5.00E-10

4.00E-10 ℎ 휆푡ℎ = 3.00E-10 2휋푚푘퐵푇 H2

2.00E-10 He Wavelength(m)

1.00E-10

0.00E+00 0 50 100 150 200 250 300 Temperature (K)

1Nobelprize.org accessed 2018 HYPER 13 Jacob Leachman • School of Mechanical and Materials Engineering Foundations: Lennard-Jones Potential 12 6     U =−4     Closest approach at rr    equilibrium Repulsion Attraction 0 σ Radius 

Energy (U) Energy  -ε o = 1.006 o = 1.0003  p  p

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 14 Foundations: Quantum Law of Corresponding States • Creates linear trends between low mass fluids Nh = A (M )1/ 2

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 15 1 Foundations: Hydrogen EOS i Ni ti di pi 1 -7.33375 0.6855 1 0 Temperature Pressure Density (K) (MPa) (mol∙L-1) 2 0.01 1 4 0 Critical Point 32.938 1.2858 15.538 3 2.60375 1 1 0 Triple Point 13.8033 0.007041 38.185 4 4.66279 0.489 1 0 x y 5 0.682390 0.774 2 0 r di t i d i t i p i ( , ) =NNii   +   exp( −  ) + i==1 i x 6 -1.47078 1.133 2 0 z 22 7 0.135801 1.386 3 0 NDdtii exp   − +   −   i i( i) i( i ) iy= 8 -1.05327 1.619 1 1 i Phi Beta Gamma D 9 0.328239 1.162 3 1 10 -1.7437 -0.194 0.8048 1.5487 10 -0.0577833 3.96 2 -- 11 -0.5516 -0.2019 1.5248 0.1785 11 0.0449743 5.276 1 -- 12 -0.0634 -0.0301 0.6648 1.28 12 0.0703464 0.99 3 -- 13 -2.1341 -0.2383 0.6832 0.6319 13 -0.0401766 6.791 1 -- 14 -1.777 -0.3253 1.493 1.7104 14 0.119510 3.19 1 --

1Leachman et al., Journal of Physical and Chemical Reference Data (2009) Jacob Leachman • School of Mechanical and Materials Engineering HYPER 16 Foundations: Cryogenic Property Models

1. Para, Ortho, Normal Hydrogen EOS 2. Para, Ortho, Normal Deuterium EOS 3. Helium-Hydrogen Mixture EOS 4. Neon-Hydrogen, Neon-Helium Mixtures 5. Methane-Ethane-Nitrogen Mixtures

-- Working on transport property scaling via residual entropy functions.

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 17 2. Engineering Applications Part 1: Para-ortho manipulation

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 18 Applications: Catalytic pressurization of liquid hydrogen fuel tanks

4 1

]

[

Excess fuel vented

]

[

]

r 3 0.75 n

h Fuel supplemented by catalyst

[

e y

t Additional fuel required h

a 2 y[i] 0.5

t w

mreq[i] r

s i

1 Addition of catalyst 0.25 t

c a

M mout[i]

r F

Orthohydrogen depleted

l o 0 0 0 100 200 300 400 M Time in Flight [hr]

Leachman et al., Advances in Cryogenics (2011) Jacob Leachman • School of Mechanical and Materials Engineering HYPER 19 Applications: Vapor-cooled shielding of Centaur LOx

A theoretical increase of 50% in cooling capacity is possible

Total energy absorbed (per mole H2)

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 20 Applications: Cryocatalysis Hydrogen Experiment Facility (CHEF)

60 ]

50 Activated Catalyst

% [

Non-Activated Catalyst

n i

a 40

i c

a 30

g 20

l o

o 10 C

0 10 20 30 40 50 60

Vspace [1/min]

Bliesner et al., AIAA Journal of Thermophysics and Heat Transfer (2012) Jacob Leachman • School of Mechanical and Materials Engineering HYPER 21 Applications: Liquid Hydrogen Fueled UAS

• Funded $20,000 on June 30th 2012 • Mission From Dean: Be the first university team to design,

build, and fly an LH2 fueled UAV.

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 22 Applications: Design - Build - Test

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 23 Jacob Leachman • School of Mechanical and Materials Engineering HYPER 24 Applications: World’s 1st 3-D Printed Cryogenic Tank

inner insulation

inner duct

outer insulation

outer duct

pressure load distribution pins

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 25 Applications: World’s 1st 3D printed cryogen tank

• 74% reduction in heat load compared to no-flow condition

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 26 Applications: Commissioned Hydrogen Liquefier @ Insitu

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 27 Applications: Hydrogen Powered ScanEagle

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 28 Applications: Low-cost liquefaction

• 80-90% of non-pipeline H2 delivered via liquid tanker truck.1 2 • LH2 will propel the early H2 economy.

• Only 8 LH2 plants in North America -Only 1 is carbon free (Niagara) -Smallest is 30 tonne/day (>50 MW) -Can only ramp 30%/day

• Production cost: $5-5.60/kgLH2

• Delivery cost: $4-12/kgLH2

Efficient, small (<1 MW), modular H2 liquefiers will increase

renewable value and enable H2 economy.

1) Technology Transition Corporation (TTC), H2 & Fuel Cells Market Report (2010) 2) Elgowainy, A., Tecnoeconomic Analysis of H2 Transmission & Distribution, DOE Workshop (2014) Jacob Leachman • School of Mechanical and Materials Engineering HYPER 29 Applications: Para-ortho manipulation via the Heisenberg Vortex Tube (HVT)

• Vortex tubes separate faster (higher T) from slower due to flow geometry • Enables para-ortho conversion to drive bulk cooling

A. Hydrogen inlet from precooler B. 77 K & 50 psi As hydrogen flows D. 50-50 o-p along tube, faster Insulation on tube wall molecules migrate forces endothermic reaction to outside to cause bulk cooling E. Hot, ortho-rich H2 F. recycled Cold H2 outlet

To 2nd vortex tube C. Catalyst along tube wall causes or J-T valve endothermic conversion of hot parahydrogen to orthohydrogen

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 30 Applications: HVT CFD Performance

CFD modeled in both COMSOL & Ansys

4 Comparison to Experiment

2 Experiment CFD with Normal Hydrogen 1

CFD with ParaHydrogen Cold Temp ColdTemp Drop[K] 0 0.2 0.3 0.4 0.5 0.6 0.7 Cold Fraction

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 31 Applications: HVT Experimental Results

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 32 Applications: HVT around the dome

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 33 Applications: Vortex LOx Separation (VorLOx)

• Vortex tubes have been demonstrated for LOx separation for air-breathing vehicles. • Dual stages were required to achieve 95% LOx purities.

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 34 Applications: Initial VorLOx results

Oxygen percentage PR ~ 2.5 in vortex effluent Tin ~ 89 K

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 35 Applications: O-P innovations since 2010 (thus far)

1. Autogenous UAV tank pressurization valve (2011) 2. Generalized O-P property models (2013) 3. First LH2 drone designed by a university (2014) 4. First 3D printed LH2 fuel tank (2015) – started Protium Innovations LLC 5. Heisenberg Vortex Tube: the first device to utilize P-O endotherm for primary cooling (2016) 6. VorLOx: magnetic separation of liquid oxygen in a vortex tube (2018)

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 36 2. Engineering Applications Part 2: de Broglie Wavelength

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 37 Applications: Predicting solid properties Hydrogen Deuterium Neon

400000 s

s 300000

e r t *=392388 - 166174 * S m

Neon

e h

S 200000

e c

u Deut erium

d e

R 100000 Hydrogen

0 0.5 1 1.5 2 Quantum Parameter

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 38 Applications: Pressurizing LH2 with Helium Tank Volume: 150.2 ft3, 573 lbm of LH2 • More helium pressurant required when injected into FWD (Ullage) Diffuser

submerged LH2 diffuser (1.52 lbm vs 0.28 lbm in ullage).

Aft (Submerged) Diffuser Fully Submerged

Figure from 2016 eCryo Industry Workshop, July 11-12, 2016, Glenn Research Center Jacob Leachman • School of Mechanical and Materials Engineering HYPER 39 Applications: World’s 1st <77 K PVT-x measurements

Rubotherm Isosorp 2000 magnetic suspension microbalance modified for cryogenics.

Conducted first ever liquid He-H2, He- Ne, H2-Ne PVT-x measurements. Developed first mixture EOS.

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 40 Applications: Experiments on Cryogenic Permeation

• Little literature except (1971) Boeing study. • Anomalous increase in permeation at low T. • No efforts to reproduce or explain.

[2] Hoggatt, J 1971. Investigation of the Feasibility of Developing Low Permeability Polymeric Films (No. ASG-2-5540). BOEING AEROSPACE CO SEATTLE WA.

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 41 Applications: Cubic Cryo Chamber Permeation Obj. (C3Po)

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 42 Applications: Initial Permeation Results

1.00E-03

1.00E-04 1 mil Ultem

1.00E-05 1 mil PET L / sec.) / L

- 1.00E-06

1.00E-07

1.00E-08

1.00E-09 Rate (mbar (mbar Rate 1.00E-10 0 50 100 150 200 Temperature (K)

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 43 Applications: Cryogenic Fuel Bladders

• Low permeation rate of bladders contradicts early experiments with critical issues.

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 44 Applications: de Broglie wavelength innovations (Pending)

1. Solid hydrogen scaling rules (2010) 2. Helium-hydrogen mixture models leading to transport & self diffusion (2016) 3. Quantum scaling of residual entropy to predict transport behavior (Pending) 4. Cryogenic permeation studies showing new potential for cryogenic liquid fuel bladders (Pending)

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 45 Community: The HOW of a Hydrogen Organized Washington

3. Pipeline to Space Jacob Leachman • School of Mechanical and Materials Engineering HYPER 46 Pipeline: Novel Fuels – H2 compounds

▪ Density of 0.9 kg/L, 9x higher than LH2 ▪ Held stable at 1 atm and 23 K ▪ Could use epitaxial growth to seed high density crystal formation.

W.L. Mao et al. “Pressure-temperature stability of the van der Waals compound (H2)4CH4,” Chemical Physics Letters 402, (2005) 66–70. Jacob Leachman • School of Mechanical and Materials Engineering HYPER 47 Pipeline: What has changed since the Saturn V?

Problems: -- “Been there, done that.” “Antiquated field.” “Too dangerous for academia.” -- “We don’t have anybody qualified to review proposals in cryogenics. We can’t fund anything in cryogenics.” -- “We can’t have cryo on the ship.” -- Hydrogen needs “four miracles; that’s unlikely… saints only need three.” -- “Hydrogen fuel cells are so bullshit.”

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 48 Pipeline: Re-informing, Re-starting, Re-imagining

A general awareness that: 1. Comprising 74% of the universe, humanity’s evolution necessitates mastery of hydrogen. 2. Space is mostly a cold, cryogenic place. 3. Cold hydrogen will be key to both our space challenges and regional renewable energy. 4. Quantum properties of hydrogen can unlock it’s potential - creating new high density fuel compounds, novel o-p refrigerators, & much more.

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 49 Thank you! http://hydrogen.wsu.edu @hydrogenprof

Jacob Leachman • School of Mechanical and Materials Engineering HYPER 50