MATERIA AT A GLANCE - spethermosets.org · • Two-part thermoset resin system • Based on...
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Transcript of MATERIA AT A GLANCE - spethermosets.org · • Two-part thermoset resin system • Based on...
MATERIA AT A GLANCE
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• A manufacturer of high performance thermoset resins with unique performance properties
• Founded in 1998
• Nobel-prize winning chemistry
• 90 US and 270 foreign patents
• World-class technical services and support
• Only resin system that utilizes Grubbs Catalyst® technology
We enable our global customer base to be more competitive in the market with…
• High Temperature Subsea Insulation and Buoyancy Products
• Tough, Downhole Tools for High Pressure and High Temperature
• High Speed and High Frequency Electronics
• Advanced Composites
THERMOSETRESINS
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CAPABILITIES AND LOCATIONSManufacturing – Huntsville, TX
Research & Development Center – Pasadena, CA
• Application engineering
• Processing & molding support
• Prototyping
• New product development
• Analytical testing
• Located 65 miles north of Houston
• Resin production
• Molded parts
• ISO 9001:2008 certified QMS
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MARKETS SERVED
Subsea Insulation
Chlorinated Fluid Handling
Downhole Tools
Electronic Materials
Subsea Buoyancy
Lightweight Pressure Vessels
Auto Composites
Proxima® HPR“super-tough”
Proxima® STR“filler-compatible”
Proxima® HTI“high-temp stability”
Proxima® ACR“advanced composites”
YouTube
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PROXIMA THERMOSETS
NORBORNENEMONOMERS
PROXIMA®
THERMOSET NORBORNENE POLYMER
• Two-partthermosetresinsystem• Basedondicyclopentadiene(DCPD)andafamilyof
norborneneco-monomers• RingOpeningMetathesisPolymerizationenabledbyMateria’s
proprietaryGrubbsCatalyst®technology• Leveragingaportfolioof15+monomersand20+metathesis
catalysts
UNREINFORCED POLYMERS
SYNTACTIC FOAMS
CONTINUOUS FIBER
COMPOSITES
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TNP NOMENCLATURE
Common Name(s) Technical Name(s) Polymer TypePEEK Polyether ether ketone ThermoplasticDCPD or poly-DCPD Polynorbornene Thermoset
Current common names for our products don’t always fit. More appropriate: Thermoset Norbornene Polymer
Our product’s trade name is:Proxima®
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PROXIMA® RESIN ATTRIBUTES
MATERIA
MARKET DISRUPTING
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THERMAL-MECHANICAL PROPERTIESProxima® resinscombinehightemperaturestabilitywithhighimpacttoughness
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10
100
1000
0 50 100 150 200 250
GlassTransitionTemp(°C)
Notched
Izod
Impact(J/m
)
Polyurethanes
HighTempEpoxies
Proxima
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PROXIMA® RESIN FAMILY
MATERIA
0
100
200
300
400
500
0 20 40 60 80 100 120 140 160 180 200
Tens
ile M
odul
us (k
si)
Glass Transition Temp (°C)
Proxima® HTI resins for high temp insulation
Proxima® ACR resins for GF and CF composites
Proxima® HPR high-performance resins
Proxima® STR resins for syntactic foams
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PROXIMA® RESINS – NOT TRADITIONAL POLY-DCPDMore Robust
Grubbs Catalysts
Fewer process controls
Fewer defects
Low odor products
Filler compatible
Broader Monomer Toolbox
High elongation monomers
Low-DCPD and DCPD-free
systems
Films / coatings with Low
dielectric Loss
Tunable, reactive functional groups
Application Engineering
Formulations designed to meet application needs
Resin/catalyst selection for cure
profile target
Composite fabrication-
friendly
Processing
RIM
Mold Casting
RTM/VARTM
PROXIMA® HIGH TEMPERATURE INSULATION RESINS
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CASE STUDY: HIGH TEMP SUBSEA INSULATION
from Miesner & LefflerOil and Gas Pipelines in Nontechnical Language
LOW WATER UPTAKE, NO HYDROLYSIS
THERMOSET ELASTOMER
LOW VISCOSITY LIQUID RESIN
Castings up to 80’ (24 m)
Low internal stress, reelable, low temperature properties
No melting point = no creep
WIDE PROCESS WINDOW
Consistent properties in all weather & process regimes
Slow: custom coating, Medium: large parts, Fast: field joints
SELECT DESIGN CRITERIA
Stable to effects of hot/wet aging
Ease of processing
MATERIA
HTI 1400 WATER UPTAKE KINETIC STUDY
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• Short duration study – Average of 3 cube sizes (1” , 1.5”, 1.75”). Cube size did not drastically alter uptake values.
• Long duration study – ASTM D638 Type I tensile specimens
TEST RESULTS:
• Very low equilibrium water content <1%
• Equilibrium is reached quickly
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
0 15 30 45 60 75 90 105 120 135 150 165 180
% W
EIG
HT
CH
AN
GE
TIME (DAYS)
SHORT DURATION UPTAKE VARIABLE TEMPERATURE
LONG DURATION UPTAKE 204 °C (400 °F)
0.0
1.0
2.0
3.0
4.0
5.0
4 38 66 93 149 204
% W
EIG
HT
CH
AN
GE
TEMPERATURE (°C)
1 DAY UPTAKE
3 DAY UPTAKE
7 DAY UPTAKE
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HTI 1400 MINI SIMULATED SERVICE TEST
THERMOMECHANICAL PROPERTY SAMPLE SET
Internal Temperature177 °C (350 °F)
AGED MINI-SSTTHERMAL
CONDUCTIVITY
RING SHEAR
PULL-OFF
TENSILE
FLEX
ACC Epoxy
PROXIMA® HTI INSULATION
NO CHANGEIN PROPERTIES
Tests: Flex, TensileThermal Conductivity, Tg
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HIGH TEMP SUBSEA INSULATION PROJECT SUMMARY
INCOMPRESSIBLE SOLID AT DEPTHS
>10,000 FT
THERMAL BARRIER BETWEEN
FLOWLINES AND SEAWATER
SAFE APPLICATION IN THE FACTORY
OR THE FIELD
Field Joints
Full-Scale Test Pipe
PROXIMA® HIGH PERFORMANCE & ADVANCED COMPOSITE RESINS
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PROXIMA® HIGH PERFORMANCE (HPR) & ADVANCED COMPOSITE (ACR) RESINS
0
100
200
300
400
500
600
75 100 125 150 175 200 225
Notched
Izod
(J/m
)
GlassTransitionTemperature(°C)
GeneralPurposeResin
ResinOptimizedforFiller
ToughenedResin
AdvancedCompositeResin
AlternativeMaterials
ACR 4100
HPR 2100
HPR 2112
HPR 2128
HPR 2012
HPR 2000 HPR
2029
ACR 4350
High Impact Polystyrene
Polysulfone
Epoxy
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PROXIMA® HPR FOR DURABILITY
Proxima® HPR 2100 Series polymers are exceptionally tough and durable with other beneficial characteristics such as corrosion resistance, ease of fabrication, and a wide use-temperature range
PROPERTY METHOD(ASTM) UNIT HPR 2100 HPR 2112 HPR 2128
Density D792 g/mL 1.03 1.04 1.04
Moisture Absorption D570 wt.% < 0.2 < 0.2 < 0.2
Tensile Strength D638 MPa 44 57 62
Tensile Modulus D638 MPa 1,760 1,970 2,230
Elongation at Break D638 % > 35 19 17
Notched Izod, 23 °C D256 J/m 510 240 133
Glass Transition Temp E1356 °C 150 173 190
Hardness D2240 - D82 D84 D85
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CASE STUDY: CASING CENTRALIZERS
Longer wells and faster completions;
Greater value in longer horizontal wells
Lower FrictionLighter Weight
Higher Ductility
drag
wei
ght
Proxima® Thermoset vs. Metals§ A casing centralizer maintains pipe in the center of
a wellbore to ensure well completion and integrity
§ In horizontal wells, drag must be reduced to facilitate completion and enable longer horizontal well drilling
§ Use HPR 2100, HPR 2112, HPR 2124 or HPR 2128
PROXIMA® CENTRALIZERS PROVIDE LOWERED COEFFICIENT OF FRICTION
AND CAN WITHSTAND WELL CONDITIONS OF >300 °F
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CASE STUDY: CORROSIVE FLUID HANDLING
• Customer needed a material with corrosion resistance to handle a process that converts sea water to Cl2, NaOH and H2 at 90 °C
• Proxima® HPR polymer provides 6+ years service lifetimes in the caustic environment of chlor-alkali electrolysis.
• The cell tops are made in a single cast using ~800 lbs of resin and part thicknesses of 1 – 5”.
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PROXIMA® RESINS FOR FILLED SYSTEMS
MATERIA
Proxima® resin systems are ultra-low viscosity, enabling the use of high filler loadings. The resin chemistry and filler selection
can significantly improve material properties.
1200x1200x
Standard resin Filler-compatible resin
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120
140
160
180
200
unfilled polymer standard resin35 vol% ceramic
microspheres
Proxima HPR 2029(filler-compatible resin)
35 vol% ceramic microspheres
Com
pres
sive
Stre
ngth
(MPa
)
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PROXIMA® ADVANCED COMPOSITE RESINS
MATERIA
Valuepropositionversusinfusionepoxy:
EFFICIENT AND ROBUST PROCESSINGLow viscosity leads to fast, defect free infusions
LONG-TERM DURABILITYBetter fatigue properties and higher transverse direction (90°) peak tensile stress and strain
DAMAGE TOLERANCESmaller impact damage zone than epoxy and higher interlaminarfracture toughness for improved safety factors
LOW WATER ABSORPTIONHydrophobic polymer matrix leads to significantly lower water absorption enabling use in more extreme environments
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PROXIMA® ACR 4100
MATERIA
POLYMER PROPERTIES METHOD(ASTM) UNIT TYPICAL
VALUE
Density D792 g/mL 1.04
Tg DSC °C 120
Compressive Strength D695 MPa 96
Compressive Modulus D695 MPa 2,160
Tensile Strength D638 MPa 69
Tensile Modulus D638 MPa 2,550
Elongation @ Break D638 % 11
Flexural Strength D790 MPa 105
Flexural Modulus D790 MPa 2,540
Fracture Toughness, KIC D5045 MPa·m1/2 2.6
COMPOSITE PROPERTIES1
0° Short Beam Strength (ILSS) D2344 MPa 63
0° Short Beam Strength (ILSS)(after 24h water boil) D2344 MPa 57
IL Fracture Toughness, GIC D55282 J/m2 1,700
Proxima® ACR4100provideslaminateswithexcellentfracturetoughness,lowwater
absorptionandaglasstransitiontemperatureof120°Corgreater.
1 LaminatespreparedbyVARTMof1200gsm unidirectionalglassfabricandcuredat120°Cfor2h.2 DatatreatmentperReederandCrews(NASA)forfracturetoughnessatcrackinitiation.
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TOUGH COMPOSITES USING A TOUGH POLYMER
DamagezoneofProxima® laminateis48%smallerthanthatoftheepoxylaminate
PROPERTY METHOD(ASTM) UNIT ACR 4100 INFUSION
EPOXY
Damage after impact3 D7136-07 mm2 403 779
1 DatatreatmentperReederandCrews(NASA)forfracturetoughnessatcrackinitiation
2LaminatespreparedbyVARTMof1200gsm unidirectionalglassfabricandcuredat120°Cfor2h
3 TestedbyDelsen TestingLaboratories
Epoxy ACR 4100
Proxima® ACR4100outperformsstandardepoxiesby5xincrackpropagationtests
PROPERTY METHOD(ASTM) UNIT ACR 4100 INFUSION
EPOXY
Fracture Toughness, KIC1 D5045 MPa·m1/2 2.6 0.5
Interlaminar Fracture Toughness, GIC
2 D55281,2 J/m2 1,700 330
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ACR 4100 – PROPERTY RETENTION & WATER ABSORPTION
MATERIA
Tg Stability (°C)
Day 0
Day 55
Day 82
Epoxylaminate 103 83 86
Proximalaminate 129 133 132
Proxima laminates absorb less water and retain properties better than market leading epoxy laminates
Salt Water Absorption Test: ~160 Days at 60 °C
0.00%
0.20%
0.40%
0.60%
0.80%
0 1000 2000 3000 4000
Wei
ght c
hang
e
Time (h)
Proxima laminate
Epoxy laminate
Nuttetal,PolymerDegradationandStability,124,(2016),35-42.
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CASE STUDY: LESS CARBON FIBER IN PRESSURE VESSELS
MATERIA
$2MMinfundingfromtheDepartmentofEnergytolowerthecostofhydrogenstoragevessels
REDUCTION IN VOIDS / DEFECTSNew tank manufacturing process of vacuum pressure infusion of dry wound forms
HIGH TOUGHNESS RESINBetter fatigue properties and off-axis properties for improved performance after cycling
NEW WINDING PATTERNSNew patterns supported by the dry-winding that may not be achievable with wet-winding
LOWER VOID CONTENT CONFIRMED
SEM images for void detection
• Composite Overwrapped Pressure Vessel (COPV) with low void content (<0.5 vol.%) is achievable through infusion
Wet-wound epoxy tank with voids (3 to 9% across 7 different regions).
Infused tank with no detectable voids across 7 regions. Evidence of resin-rich areas can be addressed through winding process.
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INTRODUCING PROXIMA ACR 4350You no longer have to sacrifice viscosity, toughness or light weight in order to get a high Tg composite
POLYMER PROPERTIES METHOD(ASTM) UNIT TYPICAL
VALUE
Density D792 g/mL 1.05
Tg DSC °C 189
Compressive Strength D695 MPa 100
Compressive Modulus D695 MPa 2,360
Tensile Strength D638 MPa 72
Tensile Modulus D638 MPa 2,700
Elongation @ Break D638 % 11
Flexural Strength D790 MPa 108
Flexural Modulus D790 MPa 2,760
Fracture Toughness, KIC D5045 MPa·m1/2 2.0
COMPOSITE PROPERTIES1
0° Short Beam Strength (ILSS) D2344 MPa 69
0° Short Beam Strength (ILSS)(after 24h water boil) D2344 MPa 65
When compared to 350 °F cure epoxies:
• Higher KIC and elongation equates to improved toughness and damage tolerance
• Lower density = lighter weight
• Lower water absorption and stable thermal performance under hot/wet aging
• Comparable Tg values in excess of 180 °C
1 LaminatespreparedbyVARTMof1200gsm unidirectionalglassfabricandcuredat200°Cfor2h.
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PROXIMA® RESIN PROCESSING METHODS
MOLD CASTING RIM/RTM VARTM CENTRIFUGAL CASTING
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PROCESSING – REACTIVITY CONTROL
MATERIA
Controlled work-time and curing from seconds to hours and even longer
0
20
40
60
80
100
120
140
0 1 2 3 4 5 6 7 8
VIS
CO
SITY
(CP)
TIME (HOURS)
WORK TIME AT 30 °C
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PROCESSING – REACTIVITY CONTROL
MATERIA
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PROXIMA® RESIN TECHNOLOGY SUMMARY
MATERIA
• The Proxima TNP chemistry can access a range of polymer space, from high elongation to high modulus.
• Pure polymer, filled, and continuous fiber composites are possible.
• Low pressure molding: low capex and high throughput
THANK YOU
www.materia-inc.com
© 2017 Materia, Inc. 60 N San Gabriel Blvd.Pasadena, CA 91107
Wesleyne GreerSenior Manager, SalesP: 832-998-4836E: [email protected]
SUPPLEMENTAL SLIDES
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PROXIMA® HIGH TEMPERATURE INSULATION (HTI) RESINS
Property Units HTI 1400 HTI 1416 HTI 1808Glass transition temp (Tg) °C 52 68 37
Impact strength J/m 95 140 641
Hardness Shore D 74 77 64
Tensile strength MPa 35 31 13
Tensile modulus MPa 1400 1052 465
Elongation at max stress % 7 7 9
Elongation at break % >75 >100 >200
Compressive strength MPa 35 28 13
Compressive modulus MPa 1115 941 421
Thermal conductivity W/m/K 0.175 0.18 0.18
Resin Viscosity cPs 5 11,000 2000
Attribute(s)
* Low viscosity for large moldings* Translucent
* Highest viscosity* UV stability* Black
* Higher viscosity* UV stability* Black* Toughness/tear resistance for complicated geometries
FOR FLOWLINES
FOR FLOWLINES, FJs, & EQUIPMENT
• Materia currently offers these products on a non-exclusive basis
• Family of products derived from similar monomer/additives
• Choice of properties & attributes based on project & application needs
• None of these products contains glass microspheres
• Very similar flow assurance and hot/wet stability
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PROXIMA® HIGH PERFORMANCE (HPR) & ADVANCED COMPOSITE (ACR) RESINS
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ELECTRICAL PROPERTIES
MATERIA
PROPERTY STANDARD UNIT VALUE
Dielectric constant (@10 GHz) ASTM D2520-13 - 2.45
Loss tangent (@10 GHz) ASTM D2520-13 - 0.0012
Surface Resistivity ASTM D257 Ohms > 9.7 x 1015
Volume Resistivity ASTM D257 Ohm-cm > 2.3 x 1016
ADVANCED PCBs
IC SUBSTRATE DIELECTRICS
