VARTM
/ RTM MATRIX RESINS Thermal Cure |
|
|
VARTM –VS– RTM
Matrix viscosity and working time are the two major differences between VARTM and RTM. For RTM, the matrix must travel through the "X" and "Y" direction of a compact reinforcement, which requires using less then 200 cps for several hours. VARTM travels on top with transport media and only needs to impregnate the "T" or "Z" direction. This requires shorter time and can take advantage of the lower temp and faster vitrification/cure time combined with reduced thermal stress.
Because RTM requires lower viscosity, higher injection temperature (typically 160ºF - 250ºF range) is required for high-end matrix resins. The slow reaction rate at injection temperature translates into long latency at ambient and below, creating a single component system. For smaller parts, faster, two component RTM resins should be used and would overlap with the slowest of VARTM matrix resins.
CONVERTERS & MODIFIERS
Epoxy based RTM and VARTM matrix technology is dominated by the converters and modifiers. All vendors use similar epoxy resins. Converters can be divided into three categories and the amine class further divided. Processing, cost, kinetics, viscosity and end composite requirements dictate the converter class.
The three chemical classes are:
Amines, Anhydrides, and Cyanates
ANHYDRIDES | |
Advantages: § Pot Life§ Cost§ Tox§ Viscosity§ Wetting§ Long process window§ Industrial pultrusion history |
Disadvantages: § Long Cure Cycle§ Long to vitrify§ React with water§ Hard to toughen§ Multiple slow cure mechanisms,§ Time and process dependent.§ No cure end point.§ No durability or fracture toughness history§ Never used for high-end composites. |
AMINES | |
Advantages: A. Cycloaliphatic § Mechanical/toughness balance§ Low temp cure /Post cure§ Easy to toughenB. Aromatic § Mechanicals§ Cure cycle§ Easy to toughen§ 30+ years pre-preg history |
Disadvantages: A. Cycloaliphatic § High toxicity§ Can carbonate with H2O & CO2§ Moderate StiffnessB. Aromatic § High Toxicity§ Could crystallize§ Viscosity |
CYANATES | |
Advantages: § Wet mechanical retention§ Large process window§ Dielectric properties |
Disadvantages: § Cost§ Could crystallize§ Cure rate is catalyst sensitive§ Sensitive to trace metal ions, H2O, Lewis Acid & Lewis BASE catalysts.§ Viscosity§ Fracture toughness- hard to toughen§ Single raw material source |
AMINES
The three classes: aromatic, cycloaliphatic, and aliphatic, result in different cure rates and end properties but cure mechanism is the same. One amine hydrogen is available for one epoxy, which is known as stoichiometric i.e.: 1:1. This mechanism is very process forgiving as there are essentially no side reactions. (without catalysts)
ANHYDRYDES
The anhydride functionality does not react with an epoxy ring and must first be broken with another functional group, usually a hydroxyl or water. In contrast to amines, anhydride reactions are multiple. Water reacts directly with anhydrides to form a di acid, which lowers Tg, and slows time and temp to cure. After anhydride ring is opened, all reactions are very slow and there is no equilibrium end point, i.e.: different time and temps will give different properties, (the significance of which is T.B.D.)
CYANATES
Cyanates are well known for their database in space and low dielectrics for radomes, but not as well known as a converter for epoxies. Cyanates will react directly with the epoxy ring to form a 5 membered oxazolidone ring along with some cyanate/cyanate to form a triazine. This epoxy/cyanate reaction to an oxazolidone is the only epoxy cure mechanism where a heterocyclic ring is formed and a residual hydroxyl is not formed which translates into greater wet strength retention and higher wet and dry mods, especially at elevated temperatures. This mechanism is most probable for achieving high-end hot wet pre-preg type properties with Vartm processing, but toughness is an issue.
CATALYTIC Epoxy/Epoxy
Small amounts of catalyst, either basic like a tertiary amine, Dicy, or imidazole family, or acidic such as a or a BF3 or BCL3 complex can be added to any epoxy to initiate or catalyze the epoxy functionality to react with itself i.e.: homopolymerize. Excellent combination of latency and cure rate can be achieved, but high temp wet and dry mods and fracture toughness are a problem
MODIFIERS AND MORPHOLOGY
Modifiers are added for viscosity reduction and greater toughness, with as little reduction in mechanicals as possible. The low viscosity requirements eliminate most modifiers used in pre-pregs, which include thermoplastic oligomers and pre-precipitated particles.
With modifier addition, the resulting morphology is critical for mechanical/toughness performance. Two phase, bi modal particle size, creates a synergistic toughening mechanism that results in enhanced fracture toughness for best toughness balance. Two converter types: anhydride and cyanates, are intrinsically difficult to develop desired bi-modal morphology.
Applied Poleramic has developed desired two-phase modifiers for all of the converter classes. With 3D stitching the second phase may not be advantageous, as modulus suffers linearly with volume of second phase.
The material engineer has choice of Matrix property balances.
TWO COMPONENT
User-friendly VARTM resins should be impregnated at 140ºF or below, with ambient the goal. The higher the required balance of mechanical and toughness properties, the less likely ambient impregnation can be achieved. 140ºF and below requires a two component system.
API supplies all converter choices, single and two-component, together with a complete balance of mechanical and toughness properties. In addition to the product line, custom matrix resins are developed to meet required specs such as BMS 8-256, 276, 8-79 and 8-168.
CONVERTER TYPE |
Cycloaliphatic Amine |
SC-1:
§ Clear, single phase, low cost matrix resin.§ Part B: two types available with different speeds.§ Post cure optional.SC-10: § Higher Tg and performance version of SC-1.§ Part B: two types available with different speeds.SC-779: § Toughest VARTM in the industry.§ Tg = 200ºFSC-13: § Used successfully in marine applications.SC-15: § Two-phase epoxy cycloaliphatic amine.§ Most widely data based Vartm/Scrimp matrix resin which includes United Defense, Army, University of Delaware, and several Phase II SBIR’s for ballistic panels.SC-79: § Meets requirements of BMS 8-79 (also 8-219 and 8-168).§ Pre preg is Hexcel F-155 (developed by API personnel).§ Tg 280° F, 250° F post cure; 320° F with 350° F post cure. |
CONVERTER TYPE |
Aromatic Amine |
SC-31:
§ Lowest cost for this high performance category.SC-31T: § Two phase toughened version of SC-31.SC-32: § Developed for general aviation§ RTM applied.SC-35: § Highest performance of this family.§ Tg 200° C with 2.4% water pick up.§ Long infusion time at 110° F |
Anhydride SC-22: Epoxy Anhydride § High end of anhydride converted epoxies.§ Tg 204° C. Excellent wet Tg and modulus retention.§ Viscosity at 75° F is 650 cps and at 85° F 300cps. Very long working time.§ 2.6% wt. gain in water boil.SC-23: § Two phase toughened version of SC-22. |
Cyanate SC-36: § Two-phase toughened.§ Wet Tg 179° C.§ Five hundred pounds VARTMed by Boeing§ Tg greater than 180° C. Very attractive for radomes where maximum electricals required.§ Dielectric Constant 2.7, Loss Tangent .01, with excellent mechanicals.§ User-friendly alternate to pure cyanate. It’s less than one half the price of pure cyanate with only very small electrical and mechanical performance reductions.§ Five hundred pounds VARTMed, Boeing.SC-38 § Great wet strength retention.§ High Tg and modulus.§ High performance.§ 1.7% wt. gain in water boil.SC-38T § Toughened version of SC-38. Increased damage tolerance with slight modulus sacrifice.
|
SINGLE COMPONENT
All require elevated cure impregnation and frozen storage.
Converter choices: Anhydrides, slow Aromatic Amines, Cyanates and Catalytic. The anhydride and cyanates are catalytically controlled and catalyst choice dictates cure rate and latency.
CONVERTER TYPE |
Aromatic Amine |
VR-6:
§ Excellent balance of mechanicals and application.§ Viscosity: 100 cps at 160° F and less then 200 cps after 6 hours.VR-6T: § Two-phase toughened version of VR-6.§ Same user friendly application time and viscosities.§ Approx. x2 the fracture toughness. |
Anhydride SC-24 § General purpose single-phase§ Tg greater then 200° C |
Cyanate VR-10: § Single phase – very stable§ Excellent wet mechanicals – Tg Dry: 380° F / Tg Wet: 320° F.§ Two-phase toughened version of VR-10.§ Tg Dry: 350° F / Tg Wet: 270° F. |
Note:
Prepreg type matrix resins have been VARTMed, if working time is adequate at injection temp, in order to preserve database. Examples are PR500 & 520 as well as 5250-4 BMI. Injection from 180-250° F is required.
SPECIALTY PRODUCTS |
SC-11 and SC11M: § Developed for United Defense (C.A.V.) exclusively for ballistic application.§ First product of any material form that would pass ballistic shock.§ Very compliant with excellent adhesion. |
Toughened Tackifier PT-1: Solution § Controlled Elastomer particles in thermoplastic epoxy.§ 50% improvement in anhydrideVARTM C.A.I.§ Supplied 30% solids in acetone spray applied.PT-1: Film § Controlled tack for preform application.PT-1: Powder § Powder spray applied.§ 80° C fuse.PT-3: Solution § Fire retardant version of PT-2.PT-3: Film or Powder |
SCRIMP EPOXY MATRIX RESINS
SC-1 |
SC-10 |
SC-779 |
SC-13 |
SC-15 |
|||
TYPE |
Clear Single Phase |
Clear Single Phase |
Toughened Two Phase |
Toughened Two Phase |
Toughened Two Phase |
||
# of Components |
2 |
2 |
2 |
2 |
2 |
||
Mix ratio of A/B (wt) |
Faster Conv. 100:22 |
Slower Conv. 100:22 |
Faster Conv. 100:22 |
Slower Conv. 100:22 |
100:30 |
100:20 |
100:20 |
Viscocity @ ambient cps |
295 |
380 |
280 |
300 |
300 |
250 |
350 |
° F Application temp |
77 |
77 |
77 |
77 |
77/300 |
77 |
77 |
*Hours to reach 700 cps @ application temp |
1.4 |
2.1 |
1.4 |
1.9 |
1.4 |
1.0 |
3.25 |
Weight/Gallon |
9.25 |
9.20 |
9.4 |
9.35 |
9.15 |
9.16 |
9.15 |
**Cure Cycle ° F |
12 + @ 77° F |
12 + @ 77° F |
12 + @ 77° F |
12 + @ 77° F |
12 + @ 77° F |
12 + @ 77° F |
1 + @ 140° F |
Post Cure Hrs / ° F |
4 @ 160 |
4 @ 160 |
4 @ 160 |
4 @ 160 |
2 @ 180 |
4 @ 160 |
2 @ 200 |
Tg Dry ° F |
180 |
176 |
210 |
205 |
195 |
185 |
228 |
Tg Wet ° F |
151 |
146 |
168 |
164 |
158 |
178 |
|
Kic Psi square inch |
3100 |
1400 |
|||||
Flex Strength/Mod Ambient psi/ksi |
14.9 / 410 |
15.3 / 400 |
18.0 / 430 |
17.8 / 430 |
16.2 / 390 |
16.8 / 390 |
19.1 / 390 |
Cost Range/ $ per lb |
4 |
4 |
4.5 |
4.5 |
5 |
5 |
7 |
% water P.U. |
3.0 |
3.2 |
2.6 |
2.8 |
2.8 |
2.9 |
1.3 |
*100 Grams at application temp ** Suggested time/temp for demolding with unrestrained post cure cycle.
Cure cycle in mold can be any cure/post cure combination.
Kic = inch lbs 1/2 in2 Wet=48hr H20 Boil Tg=RDS G' Break
COMPOSITE PROPERITIES IN TEST
(will include when available)
SCRIMP EPOXY MATRIX RESINS
SC-12 |
SC-14 |
SC-15 |
SC-22 |
SC-35 |
SC-79 |
||
TYPE |
2 Phase Acrylate Modified |
Two Phase |
Two Phase |
Epoxy/ Anhydride |
Slight Two Phase |
Two Phase Matrix |
|
# of Components |
3 |
2 |
2 |
2 |
2 |
2 |
|
Mix ratio of A/B/C(wt) |
100/80/20 |
100/30 |
100/30 |
1:1 |
100/20 |
100/40 |
|
h @ ambient cps |
450 |
400 |
350 |
650 |
13,000 |
320 |
|
Application temp/h cps |
Ambient/ 450 |
Ambient/400 |
Ambient / 350 |
85° F 300 cps |
60° C / 350 |
Ambient 320 |
|
*Hours to reach 1000 cps @ application temp |
6.5 |
4 |
3.25 |
>6 |
4.5 |
7 |
|
Weight/Gallon |
9.1 |
9.1 |
9.15 |
9.4 |
9.3 |
||
* *Cure Cycle unrestrained |
1 hr @ 60° C |
3 @ 60° C |
2 @ 60° C |
6 hr 180° F |
12 + @ 65° C |
||
Post Cure° C |
2 hr @ 90° C |
5 hr @ 100° C |
5 Hrs @ 100° C |
2 @ 350° F |
2 @ 177° C |
1 @ 350° C |
2 @ 250° C |
Tg Dry ° C |
125 |
103 |
114 |
210 |
166 |
165 |
132 |
Tg Wet |
93 |
75 |
82 |
165 |
118 |
127 |
115 |
Kic |
1275 |
1100 |
1400 |
750 |
610 |
1150 |
|
Flex Strengh/Mod Ambient ksi/msi |
19.1/450 |
18.5/400 |
19.1/390 |
16.5/480 |
21.5/480 |
23-440 |
|
Cost Range/ $ per lb |
3.5 |
3.5 |
7 |
16 |
12 |
9 |
|
% water P.U. |
1.62 |
2.1 |
1.3 |
2.4 |
2.7 |
2.3 |
*100 Grams at application temp ** Suggested time/temp for demolding with unrestrained post cure cycle.
Cure cycle in mold can be any cure/post cure combination.
Kic = inch lbs 1/2 in2 Wet=48hr H20 Boil Tg=RDS G' Break
COMPOSITE PROPERITIES IN TEST
(will include when available)