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ECF22 - Loading and Environmental effects on Structural Integrity

ECF22 - Loading and Environmental effects on Structural Integrity
Impact of Aggressive Media on the Interlaminar Shear Strength of
Impact of Aggressive
Innovative Glass Fiber Media on the Interlaminar
Reinforced Polyurea/Polysilicate Shear Strength Hybrid of
Innovative
XV Glass Fiber
Portuguese Conference Reinforced
on Fracture, PCF 2016,Polyurea/Polysilicate
Resins
10-12 February 2016, Paço deHybrid Arcos, Portugal
Resins
Thermo-mechanical Mark modeling of a high pressure turbine blade of an
Kopietzaa*, Bernd Wetzelaa
airplane
Mark Kopietz gas*,turbine
Bernd Wetzel engine
Institut für Verbundwerkstoffe GmbH, Erwin-Schrödinger-Str. 58, 67663 Kaiserslautern, Germany
a
a
Institut für Verbundwerkstoffe GmbH, Erwin-Schrödinger-Str. 58, 67663 Kaiserslautern, Germany
P. Brandãoa, V. Infanteb, A.M. Deusc*
Abstract
a
AbstractDepartment of Mechanical Engineering, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1, 1049-001 Lisboa,
Portugal
In thisb work the impact of different media (water, sodium hydroxide (NaOH), and hydrochloric acid (HCl)) especially on the
IDMEC, Department of Mechanical Engineering, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1, 1049-001 Lisboa,
In this work the impact of different media (water, sodium
interlaminar shear strength (ILSS) of glass fiber reinforced plastics hydroxide (NaOH),
(GFRP) wereand hydrochloric
explored. The ILSSacidserved
(HCl))asespecially on the
an indicator for
Portugal
interlaminar
the adhesion
c shear
CeFEMA, between strength
Departmentfibers (ILSS) of
and matrix.
of Mechanical glass fiber reinforced
Furthermore,
Engineering, plastics
the media
Instituto uptake
Superior (GFRP) were explored.
andUniversidade
Técnico, loss of non-bonded The ILSS
de Lisboa,chemicals served
Av. Roviscowere as an indicator
Pais,determined. for
1, 1049-001 Lisboa,
the adhesion
As matrices between fibers and matrix. Furthermore,
served phosphate-containing the mediaPortugal
polyurea/polysilicate uptake
resin and
(3P loss of non-bonded
Resins®) chemicals
as a reference andwere determined.
a recently developed
As matrices served
phosphate-free hybridphosphate-containing polyurea/polysilicate
resin denoted as 2P. Additionally, resin resins
the 2P hybrid (3P Resins®) as a reference
were modified by 1 vol%and a recently
of the nonionic developed
surfactant
phosphate-free
Efka® WE 3110. hybrid resin
It was denoted
found that as
the2P. Additionally,resin
phosphate-free the 2P(2P)
hybrid resins
reaches werea modified
both, by 1increased
significantly vol% of the nonionic
ILSS surfactant
and fiber/matrix
Abstract
Efka® WE 3110. It was found that the phosphate-free resin (2P) reaches both, a significantly increased
adhesion, and simultaneously, a lower media uptake compared to the 3P. These properties were further enhanced by the presence ILSS and fiber/matrix
adhesion, and simultaneously,
of the surfactant. Besides, theamarket
lower media uptakereference
established comparedresin
to theshowed
3P. These properties
a mass were further
loss indicating the enhanced
diffusion byof the presence
unfavorable
of During their
fromoperation,
the surfactant.
phosphates Besides,
the modern
the into
composite marketaircraft
the engine reference
established
media. components resinareshowed
subjected to increasingly
a mass demanding
loss indicating operating
the diffusion conditions,
of unfavorable
especiallyfrom
phosphates the high pressure turbine
the composite into the(HPT)
media. blades. Such conditions cause these parts to undergo different types of time-dependent
degradation, one of which is creep. A model using the finite element method (FEM) was developed, in order to be able to predict
© 2018 The Authors. Published by Elsevier B.V.
© the
© 2018 The
2018creepTheAuthors. Published
behaviour
Authors. of HPT
Publishedby Elsevier
blades.B.V.
by Flight data records (FDR) for a specific aircraft, provided by a commercial aviation
Peer-review
Peer-review under responsibility of Elsevier
the ECF22 B.V.organizers.
company,under wereresponsibility
used to obtainof the ECF22
thermal organizers.
and mechanical data for three different flight cycles. In order to create the 3D model
Peer-review under responsibility of the ECF22 organizers.
needed for the FEM analysis, a HPT blade scrap was scanned, and its chemical composition and material properties were
Keywords:
obtained. fiber-reinforced
The data thatplastics, interlaminar
was gathered wasshear strength,
fed into polyurea/polysilicate
the FEM hybrid resins,
model and different media resistance
simulations were run, first with a simplified 3D
Keywords: fiber-reinforced plastics, interlaminar shear strength, polyurea/polysilicate hybrid resins, media resistance
rectangular block shape, in order to better establish the model, and then with the real 3D mesh obtained from the blade scrap. The
overall expected behaviour in terms of displacement was observed, in particular at the trailing edge of the blade. Therefore such a
1. model
Introduction
can be useful in the goal of predicting turbine blade life, given a set of FDR data.
1. Introduction
©Due
2016toThe Authors.
different Published
impacts suchby as
Elsevier
frost, B.V.
roots, and soil erosion, many installed sewer pipes are damaged over time
andDue to different
Peer-review
need to under impacts such
responsibility
be repaired. ofas
thefrost,
Conservative roots,
Scientific and such
soil erosion,
Committee
methods ofas
PCF many installed
2016.
exposure sewer pipes
and complete are damaged
replacement over time
are expensive.
and need to
Therefore, thebemore
repaired. Conservative
economical shortlinermethods
method such as exposurein and
has established the complete
past years replacement are expensive.
with glass fiber reinforced
Keywords: High
Therefore, the Pressure Turbine Blade;shortliner
more economical Creep; Finitemethod
Element Method; 3D Model; Simulation.
has established in the past years with glass fiber reinforced

* Corresponding author. Tel.: +49 (0)631/2017-147; fax: +49 (0)631/2017-199.

* E-mail
Corresponding
address:author. Tel.: +49 (0)631/2017-147; fax: +49 (0)631/2017-199.
mark.kopietz@ivw.uni-kl.de
E-mail address: mark.kopietz@ivw.uni-kl.de
2452-3216 © 2018 The Authors. Published by Elsevier B.V.
Peer-review underThe
2452-3216 © 2018 responsibility of theby
Authors. Published ECF22 organizers.
Elsevier B.V.
Peer-review underauthor.
* Corresponding responsibility
Tel.: +351of218419991.
the ECF22 organizers.
E-mail address: amd@tecnico.ulisboa.pt

2452-3216 © 2016 The Authors. Published by Elsevier B.V.

Peer-review under responsibility of the Scientific Committee of PCF 2016.
2452-3216  2018 The Authors. Published by Elsevier B.V.
Peer-review under responsibility of the ECF22 organizers.
10.1016/j.prostr.2018.12.024
144 Mark Kopietz et al. / Procedia Structural Integrity 13 (2018) 143–148
2 Author name / Structural Integrity Procedia 00 (2018) 000–000

polymers (GFRP) as key repair material. For manufacturing, a glass fiber fabric mat is impregnated by hybrid resin,
and then applied on an inflatable packer which is subsequently placed at the damaged position. After blowing up the
packer and curing of the resin the resulting GFRP in the sewer pipe represents an impermeable and mechanical
resistant “pipe-in-pipe” system.
Organic/inorganic hybrid resins came up in the end of the 90’s of the last century as matrices in glass fiber
reinforced plastics for trenchless sewer repair as well as grouting materials in mining and tunneling. They impress by
their outstanding media and heat resistance.
These hybrid resins are produced by an indirect reaction between water (from water glass, WG) and isocyanate
(from polymeric methylene diphenyl diisocyanate, PMDI), further emulsified by additives. In the first step a primary
amine is built (eq. 1) which immediately reacts in a nucleophilic reaction with another isocyanate to build the
(poly)urea group (eq. 2). Released carbon dioxide is simultaneously bonded by the sodium silicate to generate
carbonate crystals and (poly)silicate particles (eq. 3)

R N C O + H2O R NH2 + CO2 (1)

O
R N C O n
R R (2)
N N
R NH2 H H n

mNa2O · nSiO2 · xH2O + mCO2 nSiO2 · (x – y)H2O + mNa2CO3 + y(H2O) (3)

Due to the water-in-oil character of both components suitable emulsifiers are deeply necessary to earn well-mixed
and highly reactive emulsions. Market established 3P Resins® (polyi-socyanates, polysilicates, phosphates) contain
organic phosphates (e.g. isopropylphenyl phosphate, tris(2-chloro-1-methylethyl)phosphate)) in different amounts [1].
Because of REACH regulations for substituting dangerous chemicals (EG 1907/2006), and furthermore, to prevent an
unfavorable diffusion of the chemically non-bonded phosphates into the environment past studies successfully focused
on replacing them either through melamine-formaldehyde [2], or epoxy [3], or vinyl ester resin [4]. However, these
substitutes are all petroleum based. This is why recent studies further focused on the replacement of organic phosphates
by functionalized vegetable oil made from renewable resources to increase the bio-content of the matrix and decrease
the greenhouse effect via reduction of CO2 emissions. Improved mechanical properties regarding bending and com-
pression stiffness were obtained [5]. Furthermore, such substituted systems have demonstrated an improved adhesion
between fibers and matrix, further enhanced through the addition of suitable coupling agents or surfactants [6].
Nevertheless, applied systems are not only stressed by abrasion in waste water but also by corrosive media, i.e.
acid or alkaline solutions. Capillary effects lead to penetration of media into the composites structure. Chemical
destruction of both, the matrix and the fiber as well as the adhesion between them may occur. This alters the load
transfer between matrix and fibers and results in less stable composites. Thus, the impact of different media on such
composites was investigated in this work.

2. Experimental
2.1. Materials and Sample Preparation
Both, 3P and 2P two-component formulations consisted of components A (WG) and B (PMDI with respective
emulsifier and additive), and they were prepared in constant volumetric ratio of 1:2. To homogenize both
components the mixture was stirred by a turbine stirrer for 1 min at 500 rpm. The necessary chemicals were used as
received, Table 1.
While for 3P Resin® component B was purchased in a premixed state, the novel 2P resin had to be mixed
manually. Thus, neat 2P consisted of Ongronat® 2500 and Lankroflex™ L (15 vol% related to whole PMDI/WG
volume). Nonionic surfactant Efka® WE 3110 with the amount of 1 vol% of was added for further modification and
improvement of the fiber/matrix adhesion.
 Mark Kopietz et al. / Procedia Structural Integrity 13 (2018) 143–148 145
Kopietz et al. / Structural Integrity Procedia 00 (2018) 000–000 3

Table 1. List of used chemicals

Comp. Name Chemical nature Viscosity η Density ρ Purchased from
[mPa·s] [g/cm³]
A PI-Liner 3P Komp. A ~50 wt% aqueous sodium silicate 600 1.55 Polinvent Ltd. (Gyál,
solution with Na2O/SiO2 ratio of Hungary)
1:>1.6 - 2.6
B (3P) PI-Liner 3P W1 Komp. PMDI / TCPP / IPPP 310-370 1.24-1.26 Polinvent Ltd. (Gyál,
B Hungary)
B (2P) Ongronat® 2500 4,4’-diphenylmethane diisocyanate 520-680 1.24 Borsodchem Zrt.
in a mixture with higher (Kazincbarcika, Hungary)
functionalized prepolymers (PMDI)
Lankroflex™ L Epoxidized linseed oil (ELO) 1,300 1.03 Akcros Chemicals Ltd.
(Manchester, United
Kingdom)
Efka® WE 3110 Ethoxylated long chain alcohol in 300 0.99 BASF SE (Ludwigshafen,
water Germany)

The ECR Glass fiber woven fabric mats with stitched tangled fibers and an area density of 1,050 g/m² were
obtained from Fluvius GmbH (Düsseldorf, Germany). The mats were hand-impregnated using a resin amount of 1.6
l/m². After impregnation the laminates were folded to two-layers with tangled fiber layers on the outside.
Subsequently, they were placed in a steel pressing tool (20 x 20 cm²) and cured under a pressure of 3 bar for 1 h at
25 °C in a Collin P 300 P/M hot press. After demolding the samples they were post-cured under ambient conditions
without pressure. From the resulting plates specimens were cut by saw to gain 20 x 10 mm² sized and 3 mm thick
samples for further testing.
2.2. Methods
Cut samples were put into different solutions 2 days after preparing. The storage was performed in two separated
runs, where deionized water (H2O) was chosen in the first run and hydrochloric acid (HCl) and sodium hydroxyl
(NaOH) solutions (each 1 molar) in the second run. At various times samples were removed for short-beam shear
(SBS) and gravimetric tests.
Short beam shear (SBS) tests were performed according to DIN 2377. These tests were carried out on a
Zwick/Roell Type 1445 universal testing machine. The gap was set to lv = 5∙h = 15 mm, and all the tests were
performed with a deformation rate of 1 mm/min. The interlaminar shear strength (ILSS) τ [MPa] was calculated by
evaluating the maximum force Fmax [N] at initial crack as well as sample width b and height h [mm] after eq. 4:

3 F
τ= ∙ (4)
4 b∙h

Gravimetric analysis was done with a weighing scale and the mass difference Δm [mg] to the initial weight was
calculated after eq. 5.

∆m = msample − msample,initial (5)

3. Results and Discussion

The overall stability of fiber reinforced composites (FRC) is generally dominated by a decent fiber/matrix
adhesion, where the interlaminar shear strength τ (ILSS) served as an indicator. In consequence of the capillary
action of the penetrating media the bonding between fibers and matrix and the load transfer may alter.
3.1. Impact of media on the interlaminar shear strength
Media storage was performed in two separated runs where the ILSS of stored samples was determined over time
compared to the ILSS of the non-stored samples (Air). In the first run deionized water (H2O) was used (Fig. 1, left), in
the second run aqueous hydrochloric acid (HCl) and sodium hydroxide (NaOH) solutions, each 1 molar (Fig. 1, right).
146 Mark Kopietz et al. / Procedia Structural Integrity 13 (2018) 143–148
4 Author name / Structural Integrity Procedia 00 (2018) 000–000

25 25
shear strength  [MPa]

20 20

shear strength [MPa]

Interlaminar

Interlaminar
15 15

10 Matrix 10 Matrix
3P 3P
2P-15ELO 2P-15ELO
2P-15ELO-1WE3110 2P-15ELO-1WE3110
5 Media
Air
5 Media
Air
H2O 1N HCl
1N NaOH

0 0
0 15 30 45 60 75 0 15 30 45 60 75
Time t [d] Time t [d]

Fig. 1. Progress of interlaminar shear strength τ of GFRP while stored in deionized water (H2O, left) and acid and alkaline solutions
(HCl/NaOH, right), respectively, compared to non-stored samples (Air)

It was found that 3P reference composites reach their final ILSS right at the beginning of storage, whereas both,
the neat and the surfactant modified 2P systems still undergo a post-curing process. Thus, the ILSS achieves its final
stage after several days. After reaching their maxima it is clear to see that 2P composites, further enhanced by the
use of the surfactant, achieve higher ILSS than 3P composites and as a consequence higher fiber/matrix adhesion.
Deionized water turned out to generally decrease the ILSS, while the 2P composites remain at a nearly constant
level, the 3P composites still loose ILSS after several days due to storage.
Negative impact of both media, acid and alkaline solutions, respectively, is clearly seen on all tested composites.
While the 3P composites directly result in decreased ILSS, 2P composites’ post-curing hides possible loss of ILSS
in the first 14 days. The ILSS of the 3P composites was strongly impacted by both solutions, whereby alkaline
media had a stronger effect than the acid solution. For both 2P composites also decreased ILSS as a consequence of
media storage was detected, however, the type of media was within statistical tolerances not crucial.
3.2. Gravimetric media uptake
Furthermore, both test runs were accompanied with gravimetric measurements. Detection of mass uptake or loss
(Δm) during media storage was investigated. It is important to mention that the 3P Resin® includes chemically non-
bonded organic phosphates which are able to diffuse into the media. Due to recent developments the 2P matrices are
made with chemically bonded emulsifiers, hence, an unfavorable diffusion was not expected. In the first run samples
were stored in deionized water (H2O), see Fig. 2, left. In the second run the samples were stored in aqueous acid
(HCl) and alkaline (NaOH) solutions, respectively, see Fig. 2, right.
The progress under water-storage clearly indicates that the 3P composites loose mass, and thus, the organic
phosphates unfavorably diffused into the media and contaminated it. The 2P composites exhibited slight media
uptake, whereby the modified system took up less media than the non-modified version. Therefore, a stronger
fiber/matrix adhesion and thus a lower capillary action are attributed.
Clearly, the 3P composites exhibited an increased loss of mass due to the unfavorable diffusion of organic
phosphates. However, it should be noted that the impact of alkaline media was much greater than that if the acid
solution. In the case of the unmodified 2P composites no clear dependence on the storage media was identifiable.
With surfactant modified 2P composites the degradation was stronger in acid solution.
After storage in acid and alkaline media, respectively, all tested composites showed a mass loss over time.
Scanning electron microscopy
For further qualitative analysis the morphologies of the non-stored composites were investigated with scanning
electron microscopy (SEM), see Fig. 3. The morphology of 3P composites exhibited nearly neat glass fibers where
only small amounts of the hybrid resin seem to adhere on the fibers (Fig. 3, left). Compared to that, the morphology
 Mark Kopietz et al. / Procedia Structural Integrity 13 (2018) 143–148 147
Kopietz et al. / Structural Integrity Procedia 00 (2018) 000–000 5

of the 2P composites exhibited clearly strong adhesion of the polymer on the fibers with partially polymer-covered
fibers (Fig. 3, right). Thus, qualitative SEM analysis confirmed the mechanical investigations regarding ILSS and
fiber/matrix adhesion, respectively.

5 5 Matrix

4 4 3P
Mass difference m [%]

2P-15ELO

Mass difference m [%]

3 3 Media
2P-15ELO-1WE3110

1N HCl
2 2 1N NaOH

1 1
0 0
-1 -1
-2 -2
-3 Matrix
3P
-3
-4 2P-15ELO
2P-15ELO-1WE3110
-4
-5 -5
0 15 30 45 60 75 0 15 30 45 60 75
Time t [d] Time t [d]
Fig. 2. Progress of mass difference Δm of ILSS samples while stored in deionized water (H2O, left) and acid and alkaline solutions
(HCl/NaOH, right), respectively, compared to non-stored samples (Air)

Fig. 3. Scanning electron microscopy of composites’ morphologies of 3P (left) and 2P (right) GFRP, respectively, with magnification x5000

Conclusion

It was shown that composites made of reference 3P Resin® possess a lower ILSS and worse fiber/matrix
adhesion than the innovative composites containing 2P resins. These investigations were further successfully
confirmed by SEM analysis. The ILSS of 2P composites could be even further enhanced by a surfactant. It is
important to mention that 2P composites undergo a post-curing process to reach the maximum ILSS. Due to media
contact the ILSS of the composites was generally decreased over time. However, no general principle could be
found how each media affects each matrix.
Gravimetric tests showed that 3P composites inherently exhibit mass loss over time, independent from the
storage media. They exhibit an unfavorable diffusion of chemically non-bonded organic phosphates into the media.
In case of water storage, the 2P composites absorb only a small amount of water what is further improved due to the
presence of the surfactant. Their storage in aggressive acid and alkaline solutions resulted in minor mass loss, which
indicated slight degradation effects.
148 Mark Kopietz et al. / Procedia Structural Integrity 13 (2018) 143–148
6 Author name / Structural Integrity Procedia 00 (2018) 000–000

Acknowledgements

The authors gratefully acknowledge the German Federal Ministry for Economic Affairs and Energy for initiating
the program ZIM (“Zentrales Innovationsprogramm Mittelstand”) and for funding of the projects “Componat”
(KF2088328SA3) and “Samba” (ZF4052317SA7). They also acknowledge the involved Partners Polinvent Ltd.
(Gyál, Hungary) and Fluvius GmbH (Meerbusch, Germany).

References

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[2] Castellà, N.; Grishchuk, S.; Karger-Kocsis, J.; Schehl, M. J. Appl. Polym. Sci. 2011, 119, 7-14.
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[4] Karger-Kocsis, J.; Erdélyi, S.; Nagy, G. J. Appl. Polym. Sci. 2007, 103, 853-859.
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[6] Kopietz, M., Bilgin, F., Grishchuk, S., Wetzel, B., Key Engineering Materials 2017, 742, 9-16.