Product Portfolio for Fiber Composite Applications

Depending on the application and desired modification, different products can be used for improving laminating and injection resins:

1.

- Improved impact resistance over a wide temperature range (easier finishing) - Damage-tolerant systems - Improved inter-laminar shear strength, better fiber adhesion - Higher pressure resistance (e.g. in pipes), reduced shrinkage

Toughening epoxy resins with copolymers (Albipox)

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2.

Toughening epoxy resins with core shell materials (Albidur)

- Improved impact resistance over a wide temperature range - Negative coefficient of expansion, significantly reduced shrinkage - Moderate viscosity increase on addition, no loss with modulus and TG

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3.

- Significantly improved modulus and flexural strength - Due to low viscosity increase, suitable for injection processes (e.g. RTM) - Lower CTE, reduced shrinkage - Improved surface quality (Class A)

Modifyingepoxy resins with nanoparticles (Nanopox F, Albipox F)

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4.

- Improved impact resistance over a wide temperature range - Damage-tolerant laminates

Modification and elastification of phenolic resins with block copolymers (Albiflex) Toughening unsaturated polyester resins and vinyl ester resins (Albidur, Hycar RLP)

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5.

- Improved impact resistance over a wide temperature range (easier finishing) - Damage-tolerant systems - Increased pressure resistance (e.g. in pipes), reduced shrinkage - Hydrophobic laminates with reduced water absorption

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1. Toughening epoxy resins with copolymers
- Improved impact resistance over a wide temperature range (easier finishing) - damage-tolerant systems - Improved inter-laminar shear strength, better fiber adhesion - Higher pressure resistance (e.g. in pipes), reduced shrinkage Product overview
Technical data (no specification)

Type

DGEBA TMP-TGDE DGEBA / Albipox 3001 15 DGEBF *) NBR = Acrylnitril-Butadien-Copolymer

Albipox 1000 Albipox 1005

NBR*) Base resin EEW Dyn. viscosity, Characterization >g/equiv.@ 25C [mPas] [wt%]
40 50 330 320 200,000 65,000 22,000

215

standard type low viscosity; contains diluents application-ready resin

Exclusively tailored, customer-specific products are also available for special applications. To modify an existing system, part of the epoxy resin is replaced by Albipox 1000 or Albipox 1005 (see also application remarks below). If blending is not possible, the ready-to-use Albipox 3001 can be employed. Improvements to properties Epoxy resins have a substantial disadvantage: Their brittleness. This disadvantage can be more than compensated by an elastomer modification (so-called "toughening" or impact resistance modification). In contrast to an elastification, the elongation at break of the cured modified resin normally remain under 10 %. The toughening of epoxy resins proves to be difficult, however. Thus, for example, the use of flexible hardeners or the addition of non-reactive flexibilizers significantly impairs a number of important properties such as tensile strength and modulus, thermal and chemical resistance as well as thermodimensional stability. These negative effects can be avoided by toughening with copolymers based on reactive elastomers. However, the pure liquid elastomers are only slightly miscible with epoxy resins, if at all. The different Albipox grades are reaction products between epoxy resins and an elastomeric copolymer. Hereby, an epoxy resin is reacted with an excess amount of the reactive liquid elastomer. After the reaction, the elastomer molecules are epoxy functional and will be chemically bonded to the resin matrix during curing. Albipox products are miscible with all epoxy resins in any ratio. Albipox products can be used by epoxy resin formulators like a modular system. There are no limitations in respect to the resins and hardeners that can be used.

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Figure 1 shows the effect of such a resin modification on the laminate. As the glass transition temperature of the liquid rubber used lies in the range -40 C to - 50 C, the significantly improved properties are also found at these lower temperatures. An additional advantage is the improved processability of the modified laminates, thereby avoiding splintering on mechanical finishing. The shrinkage is also reduced, as the rubber domains can absorb the internal stresses arising during curing
.

Figure 1: Improvement in the laminate properties through the use of toughened epoxy resins

How it works During curing, a phase separation of the elastomeric parts occurs regardless the chemical nature of the hardener and the curing temperatures. This results in finely dispersed rubber domains which are homogenously distributed across the resin. As can be seen in Figure 2, the domain size typically is in the range between 0.2 4 m. For the most part, the rubber domains consist of the relatively long molecules of the elastomer used, and are chemically bonded to the matrix via their epoxy groups at the phase boundary. If a force is now applied to the cured resin system, it can be dissipated uniformly in all directions when encountering a rubber domain.

Figure 2: Scanning electron microscope images of a rubbermodified epoxy resin

If a tear has already occurred, it is prevented from further tearing: The elastomer particles stretch perpendicular to the direction of tear and are not torn out, as they are bonded chemically to the matrix. Figure 2 shows the finely distributed elastomer particles in the epoxy matrix (see also Figure 3).

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cavitated rubber domains shear bands crack bridging

Figure 3: Schematic representation of the rubber domain under stress

Application remarks The correct ratio of rubber to epoxy is crucial for successfully improving an epoxy resin formulation. Normally, optimum results are obtained with 10 15 phr rubber (i.e. 10 15 parts rubber on 100 parts resin). Hardeners and fillers etc. are not considered. Part of the epoxy resin used in the formulation is replaced by the type of Albipox selected. The amount of hardener is adjusted to the altered epoxy equivalent weight of the new resin mixture. An adjustment is not required for non-stoichiometric hardeners such as dicyandiamide. Fillers and other recipe components are used as normal. Sample calculation for the epoxy equivalent when using Albipox 1000: Bisphenol-A standard resin (EEW 185) Albipox 1000 (EEW 330) Total mass elements EEW *) NBR = nitrile butadiene rubber

Original formulation
100 100 185

10 phr NBR 12 phr NBR 15 phr NBR

*
)

85 25 110 206

82 30 112 210

77.5 37.5 115 216

If the viscosity of the Albipox selected is too high for the mixing process used, we recommend preheating to 70 80 C.

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2. Toughening epoxy resins with core shell materials
- Improved impact resistance over a wide temperature range - Negative coefficient of expansion, significantly reduced shrinkage - Moderate viscosity increase on addition, no loss with modulus and TG Product overview
Technical data (no specification)

Type

Albidur EP 2240 40 Albidur EP 2240 A 40

Silicone con- Base tent [wt%] resin

DGEBA DGEBA

EEW Dyn. viscosity, >g/equiv.@ 25C [mPas]

300 300 35,000 35,000

Characterization
C-Silicone base A-Silicone base

Albidur EP 2240 and 2240 A differ in the silicone base: The elastomer particles in EP 2240 are based on a condensation curing silicone, while Albidur EP 2240 A is based on an addition curing mechanism. This results in a different hydrophobicity of the particles which can be utilized to adjust to the polarity of formulations. Improvements to properties Besides the low viscosity, further advantages are the high thermal stability (up to 200 C) as well as excellent electrical properties. UV and ozone stabilities are also significantly improved. In contrast to the Albipox products, UP und VE resins can also be modified with Albidur. Albidur products consist of a reactive resin in which silicone elastomer particles of a defined size (0.1 3 m) are finely distributed. The silicone elastomer particles have an organic shell structure comprising reactive groups (Figure 4). The toughening mechanism is the same as in Section 1; however, the rubber domains are already preformed and not built during the curing process.
silicone rubber shell reactive group

Figure 4: Schematic representation of an Albidur particle

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3.

Modifying epoxy resins with nanoparticles

- Significantly improved modulus and flexural strength - Due to low viscosity increase, suitable for injection processes (e.g. RTM) - Lower CTE, reduced shrinkage - Improved surface quality (Class A)

Product overview
Technical data (no specification)

Type

Base resin
DGEBA DGEBA/ DGEBF DGEBF EEC

EEW Dyn. viscosity, Characterization >g/equiv.@ 25C [mPas]

295 290 275 220 245 330 260 60,000 45,000 20,000 5,500 200 70,000 35,000

Nanopox F 400 Nanopox F 440 Nanopox F 520 Nanopox F 630 Nanopox F 640

HDDGE DGEBA/ Albipox F 080 DGEBF DGEBA/ Albipox F 081 DGEBF *) NBR = nitrile butadiene rubber Improvements to properties

special for glass, aramide and carbon fibers ; 40% SiO2 nanoparticles crystallization-free; 40 % SiO2 nanoparticles Low viscous; 40 % SiO2 nanoparticles cycloaliphatic formulations; 40 % SiO2 nanoparticles for systems with reactive diluents; 40 % SiO2 nanoparticles contains NBR and nanoparticles
*
)

contains NBR and nanoparticles

*
)

Modifying resins for fiber composites with about 10 % nanoparticles significantly enhances the mechanical properties of composites. Also, with increasing nanoparticle content the shrinkage is considerably reduced which enables a class-A surface to be attained. The CTE is also significantly reduced. Albipox F 080 or 081: If laminating or injection resins are modified with both copolymers (based on NBR) and nanoparticles, as realized in these two Albipox types, the fracture toughness can be significantly increased compared to a modification with copolymers alone. Damage-tolerant systems, e.g. for ballistic applications (armor), with a superior property profile can be designed using this approach (Fig. 5).

Control (60 J)

CTBN/nanoparticles (60 J)

Figure 5: CFRC after 60 J impact testing (unmodified / modified with Albipox F 081)

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Figure 6 shows the flexural strength of a glass-fiber reinforced composite produced using VRTM (epoxy resin, anhydride-cured, 60 % glass fiber).

Figure 6: Flexural strength of a GFC depending on the nanoparticle content

Due to their small size and the absence of any larger aggregates, the nanoparticles can easily penetrate all fiber structures (Fig. 7) without compromising the impregnation by excessive viscosity, thereby enabling all the state-of-the-art process technologies like resin infusion, RTM, or resin injection. In addition to significantly improved mechanical properties (modulus, fracture toughness), the thermal expansion, shrinkage and electrical properties can also be improved.

resin

fiber

fiber 15 % Nano How it works

resin 4 % Nano

Figure 7: SEM-Pictures of GFRCs with different levels of SiO2-nanoparticles (based on Nanopox F 400)

particle number density

20

40

particle size [nm]

60

80

100

Figure 8: Particle size distribution (Determined by SANS)

Nanopox F products are colloidal silica sols in a resin matrix with surface-modified, spherically shaped silica nanoparticles having diameters below 50 nm and an extremely narrow particle size distribution (Fig. 8). Depending on the application, colloidal silica sols are used in corresponding epoxy resins or as ready-for-use products. The spherical silica is distributed agglomerate-free in the resin matrix (Fig. 9). This results in a very low viscosity of the dispersion with SiO2 contents of up to 40 wt%.

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The nanoparticles are chemically synthesized from aqueous sodium silicate solution. In this unique process the binding agent is not damaged, in contrast to processes in which powdered fillers are dispersed with dissolvers or other equipment using high shear energy.

Figure 9: TEM images of a cured Nanopox sample with SiO2 nanoparticles

4.

Modification and elastification of phenolic resins with block copolymers

- Improved impact resistance over a wide temperature range - Damage-tolerant laminates

Product overview
Technical data (no specification)

Type

Albiflex H 1083 S1

Silicone content Base resin [wt%]

40 phenolic resin

OH-equivalent Characterization weight

200 65 % solution in methoxypropanol

Improvements to properties Albiflex H 1083 S1 is a phenolic resin silicone copolymer which is available for the modification of phenolic resins. Toughness and impact resistance of phenolic resin composites can be improved using this Albiflex type.

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5. Toughening unsaturated polyester resins and vinyl ester resins
- Improved impact resistance over a wide temperature range (easier finishing) - damage-tolerant systems - Increased pressure resistance (e.g. in pipes), reduced shrinkage - Hydrophobic laminates with reduced water absorption Product overview
Technical data (no specification)

Type

Albidur UP 6140 Albidur VE 3320

Silicone con- Base resin tent [wt%]

40 20

Properties

Glycol /ophthalic acid 20 % styrene 5,000 Bisphenol A- 30 % styrene 2,000 vinyl ester

Dyn. viscosity, Characterization 25C [mPas]

modifcation of unsaturated polyester resins modifcation of vinyl ester resins

Improvements to properties Polyester and vinylester resins can be toughened with core shell materials. A further advantage is the reduced absorption of humidity of the modified laminates.

The information contained in this publication is based on our current state of knowledge, but is unbinding and does not represent an assurance of definite properties. They also do not exempt the processor from his own tests in relation to the usability of our products for his special application purposes. The protection rights of third parties must also be observed. February 2006