2013_David Marshall_NHSC Hypersonic Materials Structures Overview

8/10/2019 2013_David Marshall_NHSC Hypersonic Materials Structures Overview

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NHSC Materials & Structu res

David MarshallTeledyne Scientific

Thousand Oaks, [email protected]

805-373-4170

Annual Review

Washington, August 6, 2013

NHSC-Materials & Structures Overview

www.nhsc-ms.net


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UC Berkeley/ALS

R. Ritchie(mechanics,imaging)Comb ine experiments and

mu lt i -scale modelsinto a

virtual test system

Comp utat ional tools

new experimental method s

new mater ials &

processing science

Teledyne Scientific

D. Marshall(materials & structures)B. Cox(mechanics of materials)

UC Santa Barbara

F. Zok(structural materials)

U. of Texas

P. Kroll(atomistics)

Missouri University

W. Fahrenholtz

G. Hilmas(UHTCs)

U. of Colorado

R. Raj(high temp.materials & properties)

U. of Miami

Q. Yang(mechanics)

Collaborations, test and advisory support

AFRL/WPAFB(M. Cinibulk, T Parthasarathy)ALS Berkeley, NASA, Boeing, ATK, Lockheed-Martin

AFOSR:A. Sayir

NASA: A. Calomino

National Hypersonic Science Center for

Materials and Structures NHSC Materials & Structu res


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Highly integrated research program: graduate students & post docs

48 journal publications; 23 plenary/keynote presentations at

international conferences (including Mueller award lecture at

ICACC'12, 4 lectures at 2012 Ceramics Gordon Conference); 21

invited presentations at conferences; 16 conference proceedings;

30 other conference papers

Organized International Summer School on Materials for

Hypersonics, UCSB, Aug. 2011

Organized International workshop on high-temperature ceramic

composites, Boulder CO June 12-15 2012www.engineceramics.org

Organized International conference on UHTCs, Austria, May 2013

Organized 7 Symposia at international meetings

Active collaborations with 10 universities

Sharing of data & modeling with AFRL, Army, NASA, Rolls Royce,

GE, DTU Denmark

NHSC-MS highlights


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Univ. of Canterbury, NZ (S. Krumdieck, Raj, Marshall):PP-MOCVD

Univ. of Queensland, Australia (M. Smart, Marshall, Zok):Fabrication, laser

testing and modeling of non-eroding ablatively cooled materials

Univ. of Virginia (E. Opila, Hilmas, Fahrenholtz, Kroll, Raj, Marshall): O18

diffusion studies in UHTCs and PDCs

von Karman Institute, SRI, U. Vermont (J. Marschall, Hilmas, Fahrenholtz):

plasmatron testing of UHTC materials SRI (J. Marschall, Raj):atomic oxygen testing of Hf-O-Si-C systems

Leoben, Austria (G Dehm, Raj):high resolution and analytical TEM of UHTC

materials

Univ. Southampton (M. Spearing, Cox): Tomography of damage in composites

Kath. Univ. Leuven (S. Lomov, Cox): composite modeling Loughborough Univ., UK (Cox): composite modeling

Univ. of Melbourne, Australia (Cox): composite modeling

RMIT, Australia (Chun, Yang): composite modeling

Tokyo Inst. Tech. (Y. Shinoda,Raj):PDC/HfO2 nanocomposite matrix

Active collaborations


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Sustained hypersonic flight at high Mach No. limited by materials:-High heat flux & heat loads

-High T, oxidation, shear, erosive conditions

-Active cooling -> very high thermal gradients

- Conditions vary with location

Materials and Structures for Propulsion Flowpath

Sharp leading edges-Very high heat flux, small area

-Active cooling/heat pipes

possible, not preferred

UHTCs- very high T, high conductivity

- limitation: oxidation resistance

Flowpath surfacesLarge area: weight critical

Active cooling in some regions

CMCs:

x3 weight reduction c.f. metals

Reduced heat flux absorbed

Selection of materials and conditions


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Thin cooled textile-based

CMCs work in extreme heatflux environments and have

potential to revolutionize

materials & structures for

hypersonics.

cool skin

hot skin

Attachment by compliant truss structure

cool skin

hot skin

Attachment by compliant truss structure

Gas flow C-SiC compositewall

Gas flow

Gas flow C-SiC compositewall

Gas flow

Morphing structures

What are the barriers to their

use?

- increase stability/life at high

temperatures: oxidation

- high fidelity modeling capability fordamage & lifetime

- improved ability to test materials

CMC s and UHTCs: limitations

UHTCs (diborides) have

temperature capability andthermal conductivity needed

for sharp leading edges &

struts

Active cooling

ZrB2: T> 2000oC


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Image microstructure

Build hierarchical

geometry generator

Port to computational

mesh for each scale

Constitutive laws

Monte Carlo predictions

- strength, temp, diffusion,

damage

New materials & processing New experimental methods Virtual test

Atomistic modelingThermal transport

StructureOxygen diffusion

Processing modeling

PP MOCVD

CVD

Liquid precursors

Material synthesis

- Processing (HP, PP-

MOCVD, PIP)- Properties

- Oxidation resistance

Synchrotron CT

- Imaging microstructure

- In situ testing/imaging

at 1500 C

Laser-based testing

- High thermal gradients

-In situ strain mapping

at high T

Doped diborides

(2000 C)Hf-PDC based CMCs

(1600 C)

Numerical methods

for discrete damage

(AFEM)

UCB

UCSB/TSC/UCB/UTA

TSC/UCSB

UCSB/Miami

Miami

UTAUCSB

MS&T U.Col, TSC

UCB/TSCUCol

MS&T

TSC

TSC, U.Col, Miami

Miami

PresentPlanned

Supply of material and/or data

PresentPlanned

Supply of material and/or data

Overview of Research Activities and

Collaborations


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NHSC Materials & Structu resDoping ZrB2to increase oxidation resistance

Discovery (Hilmas & Fahrenholtz):

-doping with W and other transition metals can reduceoxidation rate x5

What is the mechanism?

- Promote sintering and densification of ZrO2scale?

- Dissolve in glass phase and increase stability?

ZrB2Based Ceramics for Hypersonic Flight

Exper iments & thermodynamic model ing(Hilmas & Fahrenholtz)

Select dopants (phase diagrams +)

Measure oxidation kinetics/microstructure

Controlled expts.: sintering ZrO2 + B2O3and B2O3+TM ;

measure effect of TM on evaporation rate of borate glasses

Atomist ics (Krol l)

Effect of dopants on structure & stability of B2O3glasses 20 m

glass

ZrO2

+

glass

ZrB2- SiC

SiC-depleted

ZrB2


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stable composition:

B2Si2O7(with cryst.

struct.!)

enthalpy of formation from melts

structure change towards sp3-B

Atomistic modeling: B2O3-WO3-SiO2

Adding W increases enthalpy. Solubility limit ~6-10 mol% Adding W promotes tetrahedral bonding at edge of WO3

clusters

MS&T synthesizing model glasses for NMR studies

(quantify tetrahedral B)

P. Kroll(1) Amorphous structures of B2O3+ WO3

Adding Si increases enthalpy except for

composition B2O3+ 2(SiO2)

=> New stable structure, B2Si2O7?

(2) Amorphous structures of B2O3+ SiO2

metal clustering in SiO2and B2O3

(-Ta-O)5-WO6-chain

Hf, Nb, Ta, Mo, W additives in borosilicate melts

trend of metal oxide clustering

MS&T: metal segregations might cause layers &

provide oxidation barriers!?

(3) TM-oxides in B2O

3and SiO

2


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Key Findings Missouri S&T1. Studying how TM additions stabilize B2O3to higher temperatures:

Thermogravimetric analysis showed that TM additions reduce the

evaporation rate of B2O3, using W, Nb, or Zr additions Onset of B2O3evaporation shifts to higher temperatures

Lowest weight losses for Nb2O5-B2O3glasses

Molecular dynamics (MD) simulations at UTA (Kroll) predict increased

BO4units (increased glass stability) with TM additions

TM-oxide-B2O3glasses with 2, 4, and 8 mol% W, Nb, or Zr were

prepared

Glasses phase separate to produce nearly pure B2O3and crystalline TMoxides during cooling. No BO4units were identified at room temperature

using Raman or NMR.

MD models may still be correct, and the glasses need to be characterized

at elevated temperatures (NMR) to compare BO4fraction to model

predictions.

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Doping ZrB2to increase oxidation resistance


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Key Findings Missouri S&T

2. Studying how TM additions change the oxidation scale morphology: Pressureless sintering of ZrO2and ZrO2-B2O3with 4 or 16 mol% WO3

Increased ZrO2grain size and density - 16 mol% WO3most effective

Sub-stoichiometric oxide (TM stabilized?) was detected in the oxidation scale at

the interface between the ZrB2matrix and surface oxide layer.

Double oxidation of ZrB2-SiC planned (16

O2followed by18

O2),with Univ. ofVirginia (Opila), using TOF-SIMS analysis of 18O2diffusion profile in16O2oxide

to characterize oxidation kinetics. If initial experiments are successful, additional

ZrB2-TM samples will be sent for testing.

3. Testing in relevant environments:

Samples delivered to Univ. of Vermont (Fletcher) for 2nd

round of ICP testing,with improved diagnostics of evolved species, to be followed by scale thickness

and microstructural analysis.

Samples delivered toAFRL (Parthasarathy/Cinibulk)for testing in the scramjet

test rig.

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Doping ZrB2to increase oxidation resistance


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Ceramic composites (CMCs)

- C-SiC & SiC-SiC based materials

Virtual test

Micro tomography(Ritchie)

DIC (Zok)

Geometry generator(Cox)

Mesh generator(Cox)

micro tomography

(Ritchie)DIC (Zok)

AFM (Yang)

Matrix & coating

materials

Comparisons expt.DIC(Zok)

AFM (Yang)

material compositions

oxidn. behavior

oxidn. mechanisms(Raj)

Atomistics (Kroll)

- Effect of Hf on

structure & stability of

PDCs

Hf-Si-C-O-N material

system

angle interlock weaves

10 m

HfO2

reinfiltratedHf-PDC inshrinkagecrack

Hf-PDCGB phase

rigid scaffold

rigid network of

large particles

MultilayerHfO2/PDC

CVDSiC

fibertow

HfO2

Hf-PDCHfO2

1 mm0.1 m

1 m

10 m

HfO2

reinfiltratedHf-PDC inshrinkagecrack

Hf-PDCGB phase

rigid scaffold

rigid network of

large particles

MultilayerHfO2/PDC

CVDSiC

fibertow

MultilayerHfO2/PDC

CVDSiC

fibertow

HfO2

Hf-PDCHfO2

1 mm0.1 m

1 m


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New high temperature oxidation-resistant

materials for matrices & coatings

PDCs contain excess carbon

relative to stoichiometric

compositions of Si-C-N-O.

Evidence for segregated carbon networkinhibiting diffusion

Extreme reactivity during pyrolysis (800

1000oC) produces good bonding with oxides

and nonoxides

Form unusual phases with transition metaloxides, e.g. zircon, hafnon. How effective are

they in protecting against UHT oxidation?

Ionescu, Papendorf, Kleebe, Poli, Mu ller, Riedel

J. Am. Ceram. Soc., 93 [6] 17741782 (2010)

Raj, Kroll, Marshall

Hf segregation in

Hf-SiCNO powder 50 h / 1500o

C

Polymer-derived ceramics (SiCNO, SiCO)


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New high Temp oxidation-resistant

materials for matrices & coatings

Hf-SiCNO polymer-derived ceramics

Experiments & thermodynamic modeling (Raj)

Selection of dopants (bond energy considerations)

Measurements of oxidation kinetics and relation to

microstructure

Processing development and modeling to form

matrices and coatings

- 100% PDC: Molecularly mixed HfSiCNO

- nanoHfO2+ 10-20vol%PDC

- dual Phase HfO2/SiC NanoComposites

Atomistics (Kroll) Atomic structure

What are the rate-limiting diffusion paths?

What is the role of carbon sheets: barrier to diffusion or

easy path for diffusion?

What is the role of dopant atoms?

2.0m 1.5m1.5m

Defect Site

1m SiC

1500C, 10hrs

2.0m 1.5m1.5m

Defect Site

1m SiC

1500C, 10hrs

HfSiCNO Matrix (infiltration)


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Hf-SiCNO polymer-derived ceramics

Experiments & thermodynamic modeling (Raj)

Increases thermal conductivity Strength retention at 1600C

HfO2/SiC nano composites

1600o

C 100h, ambient air

Oxidation and phase transformation in HfSiCNO / HfO2 materials

HfO2(light)

HfSiO4(dark)

Unoxidized

Oxide layer

Hf-Si-C-N1500oC 1000 hours

Solubility limit of Hf and phase evolution in oxidizing & inert

environments measured

Oxidation rate in dry O2not reduced relative to SiC Ready formation of hafnon in relatively dense surface layer of

hafnon/HfO2-> potential for better performance in water vapor

environments

Evidence for improved resistance to erosion in flowing water vapor

Bubble formation at SiO2/SiC interface found to be a limiting

mechanism- bubble formation inhibited in Hf-Si-C-N-O system Modeling provides new insights:

- oxidation map defines ranges of pO2/Temp conditions for bubble

formation

- bubble nucleation critical

- role of interface/surface energies & dopants -> atomistic

calculations


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enthalpy of formation for melts

local environments &Raman-spectroscopy

Atomistic modeling

bond population paralleling Raman data

solubility limit of HfO2in SiCNO early coarsening

in B2O3DHmix 0.54 eV/HfO2, => higher solubility

CU Boulder: coarsening of HfO2-SiO2films

Solubility of HfO2in B2O3and SiO2

DHinsert

[eV]

# HfO2units added


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Virtual test studies: controlled

variations/defects in weave structure

C-SiC composite

- 2-layer angle interlock weave- CVI fiber coatings

- polymer-derived matrix

- controlled weave defects

Local

shearbands

Uniformshear

hole

Larger weft

spacing


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3 D i t t l h t i ti


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3-D microstructural characterization

& geometry generator: unit cell level

5mm

5mm

Tow cross

sectional

area

M. Blacklock, B. Cox

3-D image of C-SiC

composite

computational mesh

from geometric model

analogue of Markov

chain method for tow

axis coordinates

stochastic irregular

elliptical cylinder for

each tow

problem:interpenetration

solution:enforce known

topology of textile

Statistical description of geometryTow paths

Cross-sectional areas

Orientation of cross section

Deviations from mean

Correlation lengths

create replicas of textile

reinforcement with samestatistics as those measured

3 D X CT i t t l


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Individual fiber path within a fiber

bundle mapped

Matrix porosity measure

3D Spatial information of voids

3D spatial information of fibersfor modeling fibers in tows

Colors indicate individual

segmented fiber within the entire

bundle

3-D X-ray CT microstructural

characterization: fiber level

HiNicalon-S mini compositeH Bale

3 D i t t l h t i ti


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3-D microstructural characterization

& geometry generator

length scales > unit cell

DIC measurements to map warp

crown positions

Fourier analysis

Autocorrelation analysis for longrange variations

Spatial derivatives of deviations

from ideal weave structure

Input for geametry generator

M. N. Rossol, T. Fast, D.B. Marshall, B.N. Cox, F.W. Zok, Characterizing in-

plane geometrical variability in textile ceramic composites, 2013

M. Rossol


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Synchrotron imaging of structure and damage

5mm

5mm

Tow cross

sectionalarea 3-D microstructural

characterization &

geometry generator

ll

guidewayguideway

motor andmotor and

gearboxgearbox

X-rays

load cellload cell

furnacefurnace

sectionsection

withwith

activeactive

coolingcooling

OctopoleOctopole IR lampIR lamp

arrangementarrangement

LBNL design :LBNL design : J.NasiatkaJ.Nasiatka,,A.MacDowellA.MacDowell

ll

guidewayguideway

motor andmotor and

gearboxgearbox

X-rays

load cellload cell

furnacefurnace

sectionsection

withwith

activeactive

coolingcooling

OctopoleOctopole IR lampIR lamp

arrangementarrangement

LBNL design :LBNL design : J.NasiatkaJ.Nasiatka,,A.MacDowellA.MacDowell

crack

2D2D tomographictomographic slices with no loadslices with no load

SiC-SiC composite: RT in situloading High temperature in situ stage (1700 oC)

Resolution < 1m

Input to constitutive

law calibration in

virtual test

R. Ritchie, H. Bale,

Cox, Marshall

I it t ti i l t SiC / SiC i

t i t 1750C


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In-situ testing on single tow SiCf/ SiCmin tension at 1750C

Load Extension Curve

(Single tow 1750C)

0

20

40

60

80

100

120

140

160

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35Extension (mm)

Load

(N)

H. Bale

Bale, Haboub, MacDowell, Nasiatka, Parkinson, Cox, Marshall , Ritchie, Nature Materials, 2013

Load Extension Curve180


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In-situ testing on a three layer angle

interlock ceramic textile specimen under

tension at 1750C

False colors indicate tests carried at

ultra high temperatures.

Click on the plot to run animation

Load Extension Curve

(Textile 1750C)

0

20

40

60

80

100

120

140

160

0 0.1 0.2 0.3 0.4 0.5 0.6Extension (mm)

Load

(N)

H. Bale

Bale, Haboub, MacDowell, Nasiatka, Parkinson, Cox, Marshall , Ritchie, Nature Materials, 2013

High temperature in situ tomography


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At room temp. At 1850

C at 100N

Fiber

matrix

matrix

BN

BN

SiO2


- Increased Image resolution

SEM Image

detection of fiber coating damage

H. Bale



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SiC

SiC woven composites (25o

1750o

C)

SiCSiC single-tow mini-composites

- Influence of notches at 25o1750oC

- degradation of BN coatings at 1850oC

- controlled oxidation at 1500oC

- creep


- New in situ tests

SiO2

Damage evolution


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Damage evolution

length scales > unit cell

John Shaw

Hole in

fabric

PristineDrilled

hole

0.1% global strain

Surface profileSurface profile 0.4% strain

After failure

In situmeasurement of surface

strains by DIC

Direct correlation of crack locations

with underlying weave structure

Post-mortem cross sections for

depth information

warp & weft loading directions;

pristine and defect weave

structures; drilled holes


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Comparison of 2 D simulation


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Comparison of 2-D simulation

and in situ tomography

In situ tomography 1750oC

C i 3 D AFEM ith DIC


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Surface profile 0.05% global strain 0.1% global strain

0.2% global strain 0.4% global strain 0.61% (failure)

Comparison: 3-D AFEM with DIC

measurements of multiple crack evolution

0.1%0.05%

0.2% 0.4%


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2013_David Marshall_NHSC Hypersonic Materials Structures Overview