Investigation of Fire Resistant Polyurea...
Transcript of Investigation of Fire Resistant Polyurea...
Defence R&D Canada – Atlantic
Investigation of Fire Resistant Polyurea
SystemsFinal Report
Brenda DiLoreto and Sam DiLoretoElastochem Specialty Chemicals Inc
Elastochem Specialty Chemicals Inc37 Easton RoadBrantford, Ontario N3P 1J4
Project Manager: Brenda DiLoreto, 519-754-1678 ext 229
Contract Number: W7707-088115/001/HAL
Contract Scientific Authority: Royale S. Underhill, 902-427-3481
The scientific or technical validity of this Contract Report is entirely the responsibility of the contractor and thecontents do not necessarily have the approval or endorsement of Defence R&D Canada.
Contract Report
DRDC Atlantic CR 2009-071
October 2009
Copy No. _____
Defence Research andDevelopment Canada
Recherche et développementpour la défense Canada
This page intentionally left blank.
Investigation of Fire Resistant Polyurea SystemsFinal Report
Brenda DiLoreto
Sam DiLoreto
Elastochem Specialty Chemicals Inc
Prepared by:
Elastochem Specialty Chemicals Inc.
37 Easton Road
Brantford ON N3P 1J4
Project Manager: Brenda DiLoreto 519-754-1678 ext 229
Contract Number: W7707-088115/001/HAL
Contract Scientific Authority: Dr. Royale S. Underhill 902-427-3481
The scientific or technical validity of this Contract Report is entirely the responsibility of the contractor and the
contents do not necessarily have the approval or endorsement of Defence R&D Canada.
Defence R&D Canada – Atlantic
Contract Report
DRDC Atlantic CR 2009-071
October 2009
Approved by
Royale S. Underhill
Contract Scientific Authority
Approved for release by
Calvin V. Hyatt
Chair/Document Review Panel
c© Her Majesty the Queen in Right of Canada as represented by the Minister of National
Defence, 2009
c© Sa Majeste la Reine (en droit du Canada), telle que representee par le ministre de la
Defense nationale, 2009
Original signed by Royale S. Underhill
Original signed by Ron Kuwahara for
Abstract
DRDC Atlantic is interested in evaluating polyurea coatings for use in enclosed spaces
as damage control materials. For such applications, their fire resistant properties need to
be improved. The work reported here is divided into two parts. In Part 1, three base
polyurea formulations were developed and evaluated by cone calorimetry. The goal was
to replace portions of the organic polyurea backbone to improve the flame retardancy. The
first sample utilized an diisocyanate prepolymer with a portion of its backbone made up of
a phosphorous polyol, the second sample replaced a portion of the polyether amine with an
amine terminated polydimethylsiloxane and the third sample combined the phosphorous
polyol with the amine terminated polydimethylsiloxane. Cone calorimetry determined that
the third sample yielded the best results for lowering smoke production and increasing
time to ignition. It is believed that the phosphorous polyol and polydimethylsiloxane have
a synergistic effect in improving the flame properties.
In Part 2 of this work, the phosphorous polyol/ polydimethylsiloxane based polyurea was
used as the base formulation and various combinations of flame retardant additives were
incorporated in an attempt to further improve the flame properties. Cone calorimetry in-
dicated that the best combinations included sodium phosphate, ammonium polyphosphate
(APP)/triisocyanurate 3:1, treated graphite, urea, zeolite and melamine.
Resume
RDDC Atlantique s’interesse a l’evaluation de revetements en polyuree devant servir dans
des espaces clos comme materiaux pour limiter les dommages. Pour de telles applications,
il faut ameliorer leurs proprietes ignifuges. Le present rapport est divise en deux parties.
Dans la partie 1, on rapporte le developpement de trois formulations de polyuree de base et
leur evaluation par calorimetrie a cone. L’objectif etait de remplacer des parties du squelette
organique de la polyuree afin d’ameliorer l’ignifugation. Pour le premier echantillon, on
a utilise un prepolymere de diisocyanate avec une partie de son squelette en un polyol
renfermant du phosphore. Pour le deuxieme echantillon, on a remplace une partie de la
polyetheramine par un polydimethylsiloxane a terminaisons amines. Pour le troisieme
echantillon, on a combine le polyol renfermant du phosphore avec le polydimethylsiloxane
a terminaisons amines. La calorimetrie a cone a permis de determiner que le troisieme
echantillon conduisait au meilleur resultat pour la reduction de la production de fumee et
l’augmentation du delai avant inflammation. On pense que le polyol renfermant du phos-
phore et le polydimethylsiloxane ont des effets synergiques conduisant a l’amelioration des
proprietes ignifuges.
Dans la partie 2 du present travail, on a utilise la polyuree a base de polyol renfermant
du phosphore et de polydimethylsiloxane comme formulation de base a laquelle diverses
DRDC Atlantic CR 2009-071 i
combinaisons d’additifs ont ete incorporees afin d’essayer d’ameliorer encore plus les
proprietes ignifuges. La calorimetrie a cone a montre que les meilleures combinaisons com-
portaient du phosphate de sodium, du polyphosphate/triisocyanurate d’ammonium (3/1),
du graphite traite, de l’uree, une zeolite et de la melamine.
ii DRDC Atlantic CR 2009-071
Executive summary
Investigation of Fire Resistant Polyurea Systems: Final
Report
Brenda DiLoreto, Sam DiLoreto; DRDC Atlantic CR 2009-071; Defence R&D Canada
– Atlantic; October 2009.
Background: The demand for improved damage control materials to address blast mit-
igation has led to an interest in polyureas. Polyurea shows potential for use in retrofit
pre-existing platforms because it can be applied as a spray, has extremely fast reaction
kinetics, fast cure times and low volatile organic compounds. However, it is limited in its
use because of poor fire properties. DRDC is exploring synthetic and additive routes to
improve the polyurea flame retardancy.
A polyurea is synthesized from two components: a diisocyanate (component A) and a
diamine (component B). Elastochem Specialty Chemicals explored changing the flamma-
bility of polyurea through a synthetic route and the addition of flame retardant additives.
The first part of this work explored removing some of the organic portion of the polyurea
by changing its backbone, making the base polyurea less flammable. The second part of
this work utilized the base polyurea from Part 1 and explored the addition of flame retardant
additives.
Results: The combination of a phosphorous polyol in component A and an amine termi-
nated polymethylsiloxane in component B yielded a polyurea with improved flame retar-
dant properties. It is believed that the phosphorous and siloxane interacted to produce a
more stable char than either constituent alone.
The addition of fillers improved the flame retardancy. Treated graphite contributed to an in-
sulating layer of char which was bound to the polymer surface when combined with sodium
phosphate, ammonium polyphosphate (APP)/triisocyanurate, zeolite and melamine.
Significance of results: Although the DoD Military Specification for Standard fire and
toxicity test methods and qualification procedure for composite material systems used
in hull, machinery and structural applications (MIL-STD-2031) was not met, significant
improvements towards these targets were made. A great deal of information was discovered
regarding heteroatom substitution (both phosphorous and silicon), as well as the use of
flame retardant fillers. The organic (i.e., carbon containing) components of the polyurea
are combustible. By replacing the carbon atoms with either phosphorous or silicon, the
polymer becomes less combustible. Similarily, addition of fillers reduces the amount of
combustible material in the end product. The key is to optimize the flammability properties,
while minimizing any detrimental affects to other properties.
DRDC Atlantic CR 2009-071 iii
Future plans: Based on the success of the treated graphite, the use of aromatic polyamines
as crosslinkers will be explored. It is hoped that incorporation of the carbon rings into
the polymer backbone will help to increase the formation of the char layer, thus further
improving the polyurea flammability properties. The goal is to obtain a composite which
will mitigate blast, while not increasing the fire risk to the space where it is being used.
iv DRDC Atlantic CR 2009-071
Sommaire
Investigation of Fire Resistant Polyurea Systems: Final
Report
Brenda DiLoreto, Sam DiLoreto ; DRDC Atlantic CR 2009-071 ; R & D pour la defense
Canada – Atlantique ; octobre 2009.
Contexte : La demande pour de meilleurs materiaux pour limiter les dommages en cas
d’explosion a conduit a susciter de l’interet pour les polyurees. La polyuree presente un
potentiel d’utilisation pour la modernisation de plateformes, car elle peut etre appliquee par
pulverisation, a une cinetique de reaction extremement rapide, des temps de durcissement
courts et une faible teneur en composes organiques volatils. Toutefois, son utilisation est
limitee en raison de ses mediocres proprietes au feu. RDDC etudie des voies de synthese
et d’ajout de composes pour ameliorer les proprietes ignifuges de la polyuree.
Une polyuree a ete synthetisee a partir de deux composes : un diisocyanate (compose A)
et une diamine (compose B). Elastochem Specialty Chemicals a etudie la possibilite de
modifier l’inflammabilite de la polyuree par voie synthetique et en ajoutant des additifs
ignifuges. Dans la premiere partie du present travail, on a explore l’elimination de certaines
parties organiques de la polyuree en modifiant son squelette et rendant ainsi la polyuree de
base moins inflammable. Pour la seconde partie du travail, on a utilise la polyuree de base
ainsi obtenue et on a etudie l’addition de composes ignifuges.
Resultats : La combinaison d’un polyol renfermant du phosphore et d’un polymethyl-
siloxane a terminaisons amines a produit une polyuree aux proprietes ignifuges ameliorees.
On pense que le phosphore et le siloxane ont interagit pour produire un produit de carbon-
isation plus stable que ceux produits par les composants pris seuls.
L’addition de matieres de charge a permis d’ameliorer les proprietes ignifuges. Du graphite
traite a contribue a la formation d’une couche isolante de produit de carbonisation qui etait
liee a la surface du polymere lorsqu’il etait combine avec du phosphate de sodium, du
polyphosphate/triisocyanurate d’ammonium, une zeolite et de la melamine.
Importance des resultats : Bien que la specification militaire du MDN pour ≪ Standard
fire and toxicity test methods and qualification procedure for composite material systems
used in hull, machinery and structural applications ≫ (MIL-STD-2031) n’a pas ete satis-
faite, des ameliorations importantes pour l’atteinte de cet objectif ont ete realisees. On
a recueilli de nombreux renseignements sur la substitution d’un heteroatome (phosphore
ou silicium), ainsi que sur l’utilisation de matieres de charge ignifuges. Les composants
organiques (contenant du carbone) de la polyuree sont combustibles. En remplacant les
DRDC Atlantic CR 2009-071 v
atomes de carbone par du phosphore ou du silicium, le polymere devient moins com-
bustible. De meme, l’addition de matieres de charge reduit la quantite de matiere com-
bustible se retrouvant dans le produit final. La cle est d’optimiser les proprietes d’inflamma-
bilite tout en reduisant au minimum tout autre effet negatif sur les autres proprietes.
Recherches futures : En se basant sur le succes rencontre avec le graphite traite, on
etudiera l’utilisation de polyamines aromatiques comme agents de reticulation. On espere
que l’incorporation de noyaux carbones dans le squelette du polymere contribuera a aug-
menter la formation d’une couche de produit de carbonisation, ameliorant ainsi encore plus
les proprietes d’inflammabilite de la polyuree. L’objectif est d’obtenir un composite qui
limitera les effets d’une explosion sans accroıtre les risques dans l’espace ou il est utilise.
vi DRDC Atlantic CR 2009-071
Table of contents
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i
Resume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i
Executive summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
Sommaire . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
Table of contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
List of figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viii
List of tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viii
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 Part 1 — Inorganic substitution of polyurea backbone . . . . . . . . . . . . . . . 3
2.1 Polyurea synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3 Part 2 — Fire resistant fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1 Filled polyurea preparation . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4 Conclusions and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Annex A: MSDS & Data Sheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Annex B: ACT Labs FTIR Spectra of Base Polyureas . . . . . . . . . . . . . . . . 25
Annex C: In-house Flame Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Distribution list . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
DRDC Atlantic CR 2009-071 vii
List of figures
Figure 1: Basic polyurea synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . 1
Figure 2: Cross-section images of the filled polyurea samples. All images are
the same scale. Film thicknesses are 2.1–2.5 mm, with P2P2S6 being
the thickest. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Figure 3: Example of a sample from the benchtop burn tests. . . . . . . . . . . . 10
Figure 4: Comparison of time to ignition (s) for Part 1 and Part 2 . . . . . . . . . 10
Figure 5: Comparison of peak heat release rate (kW/m2) for Part 1 and Part 2 . . . 11
Figure 6: Comparison of average heat release rate (kW/m2) for Part 1 and Part 2 . 11
Figure 7: Comparison of smoke factor (× 103) for Part 1 and Part 2 . . . . . . . . 12
Figure 8: Comparison of mass loss rate (g/m2s) for Part 1 and Part 2 . . . . . . . 12
List of tables
Table 1: Cone calorimetry results for Part 1 . . . . . . . . . . . . . . . . . . . . 5
Table 2: DMA results for Part 1 . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Table 3: Description of fire resistant fillers used in Part 2 . . . . . . . . . . . . . 7
Table 4: Formulation of samples for Part 2 . . . . . . . . . . . . . . . . . . . . . 8
Table 5: Cone calorimetry results for Part 2. . . . . . . . . . . . . . . . . . . . . 13
Table 6: DMA results for Part 2. . . . . . . . . . . . . . . . . . . . . . . . . . . 14
viii DRDC Atlantic CR 2009-071
1 Introduction
With increasing concern over the threat from improvised explosive devices (IED), interest
in materials that can be retrofitted to land vehicles and ships for increased survivability has
grown. One possible material is polyurea. The advantages of polyurea are its extremely
fast reaction kinetics, fast cure times and low volatile organic compounds (VOC).
Polyureas are synthesized using a two component system. The first component (A) is a
diisocyanate. The second component (B) is a diamine. The molecular weight, degree of
functionality and level of heteroatom substitution in these components can be chosen to
tailor the properties of the final polyurea.
The use of polyurea coatings has increased in popularity since the early 1980’s, although
their applications have been somewhat limited due to poor flame properties. Defence R&D
Canada is interested in evaluating polyurea coatings for use in enclosed spaces. The work
presented here continues from previous work [1] and further investigates synthetic methods
for improving the flammability properties of polyureas. This study has two parts. In
Part 1, a portion of the organic material of the polyurea backbone was replaced with a
phosphorous polyol and/or an amine terminated polydimethylsiloxane. The flammability
properties of the resulting polyureas were examined using cone calorimety. The optimum
polyurea formulation was then used in Part 2 to prepare a series of polyurea formulations
containing various flame retardant additives. The flame retardants included combinations
of minerals, intumescent systems, and graphite.
Fourier transform infrared spectroscopy (FTIR) was used to characterize the new poly-
mers using the phosphorous polyol and amine terminated polydimethylsiloxane precursors.
Cone calorimetry (ASTM E 1354) was used to determine the time to ignition, peak heat
release rate (HRR), smoke evolution, mass loss rate and total heat release [2]. Ideal
materials would have a long time to ignition and a reduced HRR, and the addition of a
fire retardant should not yield more smoke.
The time to ignition measures the ability to ignite a material at a specific heat flux. It
is related to the volatility of the degradation products and the time required to reach the
critical fuel concentration in the vapour over the specimen. Time to ignition gives an
indication of the time available for personnel to escape a space prior to flashover. The
Figure 1: Basic polyurea synthesis.
DRDC Atlantic CR 2009-071 1
DoD military (navy) specification (MIL-STD-2031) for minimum time to ignition with a
radiant heat of 50 kW/m2 is 150 s [3]. Peak HRR influences the rate of burning and the
rate of mass loss and determines whether the surrounding materials will ignite. The peak
HRR can be used as an indication of the degree to which a material will burn at its highest
rate of combustion [4]. The MIL-STD-2031 sets a maximum peak HRR of 65 kW/m2 as
determined using cone calorimetry with a radiant heat source of 50 kW/m2 [3,4]. Samples
of each formulation were also submitted to Defence R&D Canada — Atlantic for dynamic
mechanical analysis (DMA) and differential scanning calorimetry (DSC).
2 DRDC Atlantic CR 2009-071
2 Part 1 — Inorganic substitution of polyurea
backbone
In Part 1 of this research the focus was on the base polyurea formula. Various combinations
of inorganic material were used to replace portions of the organic backbone in an attempt
to improve the fire resistant properties of the unfilled polyurea, specifically the time to
ignition, peak heat release rate (HRR) and the total smoke released.
A review of available phosphate containing polyols and amine terminated polydimethyl-
siloxanes was performed to find suitable materials that could be used in the base formula.
The substitute in the diisocyanate portion (i.e., component A) must be a liquid at room
temperature and suitable for making a stable prepolymer with the diisocyanate. Many of
the available phosphorous polyols are solid at room temperature (e.g., Struktol R© Polydis R©
3710) or are cut with solvent (e.g., Stuctol R© VP 37452 S). These are not appropriate for this
application. These and other phosphorous polyols were also too high in molecular weight
(<500 g/mol is required) and therefore would not be incorporated into the prepolymer
properly. An approximate viscosity of 500 cps is also required so that if fillers were added,
the material could still be put through a static mixer. Exolit 550 was one possible material,
however the viscosity was too high (i.e., 3500 cps). Exolit OP 560 phosphorous polyol from
Clariant Pigments and Additives division was selected. It is a liquid at room temperature,
has a low viscosity and has a molecular weight of 250 g/mol. The supplier’s website and
sales representatives were consulted in order to determine the best available product to meet
the criteria above. The diisocyanate that was reacted with the Exolit OP 560 was Mondur
M (4,4′-methylene diphenyl isocyante) (Bayer).
Previous work used a base polyurea formula which had 15% of the organic amine in com-
ponent B replaced with a phosphorous polyol (Exolit OP 560) [1]. The cone calorimetry
showed an improvement to the peak heat release rate (from 1252 Kw/m2 for the polyurea
formula with no phosphorous polyol to 761 Kw/m2 for the polyurea with 15% phosphorous
polyol), however the total smoke increased from about 17 m2 to about 28 m2 when the
phosphorous polyol was used. That study concluded that because the reaction of the
diisocyanate with the amine is orders of magnitude faster than the reaction of isocyante with
the phosphorous polyol, there may have been unreacted phosphorous polyol that would
cause a large amount of smoke when burned and thus increase the total smoke in the cone
calorimetry testing.
In the work presented here, component A utilized the same phosphorous polyol (i.e.,
Exolit OP 5600), reacted with the diisocyanate (i.e., Mondur M) to form a prepolymer in
an attempt to ensure all of the polyol was reacted. The prepolymer was then used with the
usual component B amine (i.e., Ethacure). This was identified as P2P1S1 (P2 for project 2,
P1 for Part 1 and S1 for sample 1).
DRDC Atlantic CR 2009-071 3
Another approach for replacing organic portions of the polyurea formulation was to replace
the polyether amine portion of component B with an amine terminated polydimethylsilox-
ane of similar molecular weight in the base formula. For replacing the polyether amine
the material must be amine terminated and have a similar molecular weight to D2000.
DMS-A15 (Gelest Inc.), an amine terminated polydimethylsiloxane, was selected. This
was identified as P2P1S2.
The third sample utilized component A of P2P1S1 (i.e., Exolit OP 560) and component B
of P2P1S2 (i.e., DMS-A15) to investigate if greater improvements to the flame retardancy
could be achieved by combining both approaches.
The three different base formulations were prepared and submitted to DRDC Atlantic for
physical testing (i.e., Cone Calorimetry, DSC, and DMA). Samples were also submitted to
Actlabs for characterization via FTIR (Annex B).
2.1 Polyurea synthesis
The three samples that were prepared were (molar percents):
P2P1S1: component A: 50% 4,4′-MDI (Pure) Mondur M
50% Exolit OP 560
component B: 30% Ethacure 100/300
70% D2000/T3000/T5000
P2P1S2: component A: 100% Rubinate 9009
component B: 30% Ethacure 100/300
70% DMS-A15
P2P1S3: component A: 50% 4,4′-MDI (Pure) Mondur M
50% Exolit OP 560
component B: 30% Ethacure 100/300
70% DMS-A15
For P2P1S1, the component A was prepared by adding 2 mols of 4,4′-MDI (Mondur M)
into a mixing vessel at 40◦C, 1 mol of Exolit OP 560 was added slowly to the vessel.
The ingredients were mixed at 60 RPM with a paddle blade mixer for 5 minutes. The
temperature rose to 80◦C and was held at this temperature for two hours by placing it in
the oven. The resin was then allowed to cool.
For component B of the polyureas, approximately 200 g of material was prepared by
weighing 60 g of the Ethacure and 140 g of the D200/T300/T500 or DMS-A14 depending
which sample (i.e., P2P1S1 or P2P1S2) was being made. The material was mixed for
1 minute using a low speed paddle mixing blade (500 RPM) at room temperature and
normal pressure.
4 DRDC Atlantic CR 2009-071
Table 1: Cone calorimetry results (ASTM E1354) for Part 1 with a radiant heat source of
50 kW/m2. (Testing by Bodycote Testing Group)
Sample ID Time to
Ignition
(s)
Peak
Heat
Release
Rate
(kW/m2)
Average
Heat
Release
Rate
(kW/m2)
Total
Smoke
(m2)
Smoke
Factor
(× 103
kW/kg)
Peak
Mass
Loss
Rate
(g/m2s)
MIL STD 2031 150 60 n/a n/a 6.5 n/a
Base polyurea 21 1252.0 237.4 17.2 657 43.89
(no phosphorous or
polysiloxane)∗
Base polyurea 21 760.6 310.0 28.3 474 33.56
(containing 15% of
phosphorous polyol
in component B)∗
P2P1S1 11 286.3 133.0 27.2 256 21.14
P2P1S2 14 542.4 144.3 21.8 433 23.11
P2P1S3 16 351.9 69.8 9.1 245 22.95∗ data taken from previous work [1].
Components A and B were prepared separately, then 200 g of each were loaded into 200 mL
side by side cartridges and dispensed through an 18 element, 14
′′static mixing tube into
2 mm and 3 mm thickness sheet sample moulds. This was done at room temperature using
a hand held dispensing gun.
All sample sheets were post cured, in an oven, for 16 hours at 65◦C at normal atmospheric
conditions. Samples for cone calorimetry, DMA and DSC were cut from the cured sheets
using a band saw.
2.2 Discussion
Results of the cone calorimetry for Part 1 are outlined in Table 1. Shown are: Time to
Ignition, Peak Heat Release Rate (HRR), Average Heat Release Rate (HRR), Total Smoke,
Smoke Factor (which is calculated by multiplying the total smoke released at 300 s by the
peak HRR) and Peak Mass Loss Rate.
By examining the cone calorimetry results in Table 1, it can be seen that P2P1S3 (con-
tained a diisocyanate/phosphorous polyol prepolymer reacted with an amine terminated
polydimethylsiloxane) gave the best overall results. It had the longest time to ignition
(16 seconds), and the least smoke released (9.1 m2). Although P2P1S3 had a slightly higher
peak HRR than P2P1S1, its average HRR 69.8 kW/m2, was the lowest of the three samples.
DRDC Atlantic CR 2009-071 5
Table 2: DMA results for Part 1, at 1 Hz, 25◦C. (Testing by DRDC Atlantic/Dockyard
Labortory (Atlantic))
Sample ID Young’s Modulus
(MPa)
P2P1S1 158.1
P2P1S2 181.6
P2P1S3 2539
The peak HRR for P2P1S3 was much lower than the base material of previous work [1],
which also contained phosphorous polyol, but added into component B. The difference
between these two approaches was that in the previous work, the polyol was reacted into
the polyurea during the crosslinking stage, while in the current study, it was reacted with
the diisocyanate of component A to yield a prepolymer which was subsequently reacted
to form the completed polyurea. The improved flammability performace observed in the
current work was likely due to the phosphorous polyol being completely reacted into the
polymer, at higher loading levels; increased from 7.5% in the final polymer in the previous
work [1] to 25% in the final polymer in this work. P2P1S3 was selected to be the base
formulation for Part 2 of this study.
The smoke values for P2P1S1 and P2P1S2 were 27.2 m2 and 21.8 m2 respectively. It
was believed that reacting the phosphorous polyol with the diisocyanate to produce a
prepolymer would contribute to decreasing the smoke value from previous work [1]. The
smoke value however, is still high for both samples. The smoke value for P2P1S3 was less
than half of P2P1S1 and P2P1S2. It can be concluded that phosphorous polyols produce
higher smoke values in the material whether as a reactant in component B, or reacted in
the component A prepolymer. The current work also shows a synergistic effect between
phosphorus and siloxane when they are contained in the backbone of the polymer. One
theory for this, is that during the combustion process the phosphorous and siloxane interact
to produce a more stable char than either of them individually, thus reducing the total smoke
released.
Results of the DMA testing performed at DRDC Atlantic, for Part 1 are listed in Table 2.
The FTIR spectra are shown in Annex B. The polyurea from previous work, with no
phosphorous or polysiloxane, had a storage modulus of 203.6 MPa (at 25◦C) [1]. The
samples with only one component substituted show lower moduli. When both components
are substituted, there is a drastic increase in modulus.
6 DRDC Atlantic CR 2009-071
3 Part 2 — Fire resistant fillers
The second part of this work focused on adding fillers to the base polyurea that was selected
in Part 1 (i.e., P2P1S3 — Exolit OP 560 substituted diisocyanate and DMS-A15 substituted
polyether amine) in order to improve fire resistant characteristics. The results from previous
work showed that a combination of flame retardants was required to obtain the best results
[1]. The additives explored in the current work are listed in Table 3.
Table 3: Description of fire resistant fillers used in Part 2
Additive Description
sodium phosphate Recochem
Polybor R© disodium octaborate tetrahydrate from US Borax
ammonium sulfate Canada Colours and Chemicals
APP/triisocyanurate (3:1) internally blended
treated graphite expanded graphite flakes #1721 from Ashbury An-
thracite Industries
urea Sylvite
ammonium phosphate Rhodia
sodium bicarbonate Canada Colours and Chemicals
APP ammonium polyphosphate
Zeolite 3A Intumax AC-2
melamine 3ST Powder from Zeochem
melamine-phosphate Melapur 200 from Ciba
calcium phosphate blend 1:1 blend of calcium phosphate and ammonium phos-
phate from Canada Colours and Chemicals
talc Cantal 490 from Canada Colours and Chemicals
3.1 Filled polyurea preparation
From Part 1, P2P1S3 was selected as the base polyurea formulation for Part 2. Again values
are molar percents.
component A: 50% 4,4′-MDI (Pure) Mondur M
50% Exolit OP 560
component B: 30% Ethacure 100/300
70% DMS-A15
The base resins for components A and B were produced as outlined in §2.1. The powders
were weighted and added, according to the percentages in Table 4, to both component A
and B. For Sample P2P2S1, for example; since 200 g is used in each side of the side by
side cartridges, 5 g of sodium phosphate, 75 g of ammonium sulphate, 10 g of melamine,
10 g of calcium phosphate blend and 5 g of talc would be added to 100 g of the base resin
DRDC Atlantic CR 2009-071 7
Table 4: Formulation of samples for Part 2
Sample ID Formulation
P2P2S1∗ 2.5% sodium phosphate, 35% ammonium sulfate, 5% melamine, 5%
calcium phosphate blend, 2.5% talc
P2P2S2 4% sodium phosphate, 4% Polybor R©, 4% ammonium sulfate, 4%
APP/triisocyanurate 3:1, 4% treated graphite, 4% urea, 4% ammonium
phosphate, 4% sodium bicarbonate, 4% APP, 4% zeolite, 4% melamine
P2P2S3 10% sodium phosphate, 10% ammonium sulfate, 10%
APP/triisocyanurate 3:1, 4% treated graphite, 2% zeolite, 4%
melamine
P2P2S4 10% sodium phosphate, 10% APP/triisocyanurate 3:1, 8% treated
graphite, 8% urea, 2% zeolite, 4% melamine
P2P2S5 10% APP/triisocyanurate 3:1, 6% treated graphite, 6% urea, 6% ammo-
nium phosphate, 6% sodium bicarbonate, 2% zeolite, 4% melamine
P2P2S6 30% sodium phosphate, 4% sodium bicarbonate, 2% zeolite, 4%
melamine
P2P2S7 10% sodium phosphate, 20% ammonium sulfate, 4% treated graphite,
4% melamine, 2% calcium phosphate blend, 2% talc
P2P2S8 10% sodium phosphate, 10% ammonium sulfate, 5%
APP/triisocyanurate 3:1, 4% treated graphite, 2% zeolite, 4%
melamine, 2.5% calcium phosphate blend, 2.5% talc∗ same filler ratios that performed the best from previous work [1].
to give the desired final concentration . The powders were added to both component A and
B so that the 1:1 ratio static mixer cartridges could be used.
The powders were mixed using a high speed shear mixer at 2500 RPM. Components A
and B were then loaded into 200 mL side by side cartridges and dispensed through 18
element, 14
′′static mixing tubes into 2 mm and 3 mm sheet sample moulds using a hand
held dispensing gun. All weighing and mixing was done at room temperature. Sample
sheets were post cured in an oven for 16 hours at 65◦C at normal atmospheric conditions.
The samples for cone calorimetry, DMA and DSC were then cut from the sample sheets
using a band saw. Figure 2 shows each of the eight samples in cross-section.
Sample pucks of polyurea containing various additive materials and combinations were
produced using the same methodology as the sheet samples. The pucks were burned at
Elastochem using a flame (1100◦F), produced by a propane torch. The flame was held
on the puck for 30 seconds and then removed. The amount of smoke, change in weight
after burning, time to ignition and the formation of the char was observed (the results were
qualitative only).
8 DRDC Atlantic CR 2009-071
(a) P2P2S1 (b) P2P2S2
(c) P2P2S3 (d) P2P2S4
(e) P2P2S5 (f) P2P2S6
(g) P2P2S7 (h) P2P2S8
Figure 2: Cross-section images of the filled polyurea samples. All images are the same
scale. Film thicknesses are 2.1–2.5 mm, with P2P2S6 being the thickest.
3.2 Discussion
Qualitative observations from the in-house fire testing are included in Annex C. An exam-
ple of the burned pucks can be seen in Figure 3. The observations of the in-house fire testing
were used to determine which samples would be explored further using cone calorimetry.
The combinations which produced a good char (i.e.,not flakey), that was bonded to the
unburned polyurea, had very little weight loss after burning, had a slow ignition time,
extinguished quickly and had a low amount of observed smoke were selected. The cone
calorimetry results are listed in Table 5. Shown are; Time to Ignition, Peak Heat Release
Rate, Average Heat Release Rate, Total Smoke, Smoke Factor (which is calculated by
multiplying the smoke at 300s by the Peak heat release rate) and Peak Mass Loss Rate.
The data for Part 1 and Part 2 is presented in Figures 4–8.
DRDC Atlantic CR 2009-071 9
Figure 3: Example of a sample from the benchtop burn tests.
0
5
10
15
20
P2P
1S
1
P2P
1S
2
P2P
1S
3
P2P
2S
1
P2P
2S
2
P2P
2S
3
P2P
2S
4
P2P
2S
5
P2P
2S
6
P2P
2S
7
P2P
2S
8
Tim
e to ignitio
n (
s)
Figure 4: Comparison of time to ignition (s) for Part 1 and Part 2, heat flux 50kW/m2.
10 DRDC Atlantic CR 2009-071
0
100
200
300
400
500
P2P1S1
P2P1S2
P2P1S3
P2P2S1
P2P2S2
P2P2S3
P2P2S4
P2P2S5
P2P2S6
P2P2S7
P2P2S8
Peak Heat Release Rate (kW/m2)
Fig
ure
5:
Com
pariso
nof
peak
heat
releaserate
(kW
/m2)
for
Part
1an
dP
art2,
heat
flux
50kW
/m2.
0
50
100
150
200
250
300
P2P1S1
P2P1S2
P2P1S3
P2P2S1
P2P2S2
P2P2S3
P2P2S4
P2P2S5
P2P2S6
P2P2S7
P2P2S8
Average Heat Release Rate (kW/m2)
Fig
ure
6:
Com
pariso
nof
averag
eheat
releaserate
(kW
/m2)
(s)fo
rP
art1
and
Part
2,
heat
flux
50kW
/m2.
DR
DC
Atla
ntic
CR
20
09
-07
11
1
0
50
100
150
200
250
300
P2P1S1
P2P1S2
P2P1S3
P2P2S1
P2P2S2
P2P2S3
P2P2S4
P2P2S5
P2P2S6
P2P2S7
P2P2S8
Smoke Factor (X 103 kW/kg)
Fig
ure
7:
Com
pariso
nof
smoke
factor
for
Part
1an
dP
art2,heat
flux
50kW
/m2.
0 5
10
15
20
25
P2P1S1
P2P1S2
P2P1S3
P2P2S1
P2P2S2
P2P2S3
P2P2S4
P2P2S5
P2P2S6
P2P2S7
P2P2S8
Mass Loss Rate (g/m2s)
Fig
ure
8:
Com
pariso
nof
mass
loss
rate(g
/m2s)
for
Part
1an
dP
art2,heat
flux
50kW
/m2.
12
DR
DC
Atla
ntic
CR
20
09
-07
1
Table 5: Cone calorimetry results (ASTM E 1354) for Part 2 with a radiant heat source of
50 kW/m2. (Testing by Bodycote Testing Group)
Sample ID Time to
Ignition
(s)
Peak
Heat
Release
Rate
(kW/m2)
Average
Heat
Release
Rate
(kW/m2)
Total
Smoke
(m2)
Smoke
Factor
(× 103
kW/kg)
Peak
Mass
Loss
Rate
(g/m2s)
MIL STD 2031 150 65 n/a n/a 6.5 n/a
Base Polyurea∗ 16 351.9 69.8 9.1 245 22.95
(P2P1S3)
P2P2S1 15 301.6 102.6 18.0 135 16.87
P2P2S2 15 222.0 127.3 17.1 103 12.21
P2P2S3 12 207.9 105.7 13.4 90 12.03
P2P2S4 13 164.1 99.2 9.3 55 9.76
P2P2S5 15 202.2 118.4 12.1 76 11.21
P2P2S6 10 449.5 262.4 24.7 280 22.36
P2P2S7 11 205.2 116.8 11.9 81 12.29
P2P2S8 14 199.6 115.5 14.5 83 10.92∗ data taken from Part 1 of the current work.
From Table 5, it can be seen that P2P2S4 performed the best with a peak HRR of 164 kW/m2,
a smoke factor of 55,000 kW/kg and a mass loss rate of 9.76 g/m2s. The peak extinction
area, 498 m2/kg was about 50% less than the base polyurea (P2P1S3). The total smoke
released was 9.3 m2 which is the same (within error) as the result from the base with no
fillers.
All samples in Part 2 performed better than the base polyurea with no fillers (P2P1S3) in
terms of peak HRR except sample P2P2S6. This may be due to there being very little
carbon in the backbone of the polymer, and with no added graphite there is little carbon
present to form char. Sample P2P2S6 performed the worst with an increase in peak HRR
of 28%, a decrease of 38% for time to ignition and an increase in total smoke released of
170%. Sample P2P2S4 had the highest concentration of treated graphite (i.e., 8%), and it
is believed that this is why it gave the best result. The graphite by itself is powdery after it
is burned and creates an insulating layer that is slightly expanded away from the polyurea
surface. It is believed to be the combination of the sodium phosphate, APP/triisocyanurate,
zeolite and melamine that stabilizes this layer and keeps it attached to the polyurea surface.
The Results of the DMA testing for Part 2, which was performed by Defence R&D Canada,
are listed in Table 6. The addition of fillers up to 30 wt.% resulted in stiff, brittle samples.
The corresponding increase in storage modulus reflects this.
DRDC Atlantic CR 2009-071 13
Table 6: DMA results for Part 2, at 1 Hz, 25◦C. (Testing by DRDC Atlantic/Dockyard
Laboratory (Atlantic))
Sample ID Young’s Modulus
(MPa)
P2P2S1 799±97
P2P2S2 592±177
P2P2S3 400±155
P2P2S4 346±6
P2P2S5 801±148
P2P2S6∗ –
P2P2S7 526±49
P2P2S8 756±219∗P2P2S6 was too brittle to test.
14 DRDC Atlantic CR 2009-071
4 Conclusions and future work
Part 1 of the work reported here explored removing or substituting the organic back bone
of the base polyurea formulation in an effort to improve their fire retardant properties.
The sample yielding the best cone calorimetry results was P2P1S3, which resulted from
the reaction of the phosphorous polyol/diisocyanate prepolymer and the amine terminated
polydimethylsiloxane. Part 2 of this work explored the use of flame retardant fillers to
further improve the flammability properties of P2P1S3. The best results were observed
with the addition of graphite (layered carbon). In combination with synergists such as
sodium phosphate, APP/triisocyanurate, zeolite and melamine, stable chars were achieved.
All of the formulations were designed to be sprayed using a high pressure impingement
technique, that limits the viscosity of the material to less than 2000 cP. A low viscosity
limits the quantity of fillers (e.g.,treated graphite) that can be added to the formulations. If
the equipment can be modified to handle greater viscosities, the use of larger concentrations
of treated graphite can be investigated.
Future work should investigate the use of aromatic polyamines as crosslinkers. It has been
shown [5] that these organic rings increase the formation of the char layer which in turn
lowers the peak HRR.
DRDC Atlantic CR 2009-071 15
References
[1] DiLoreto, B. and DiLoreto, S. (2008), Fire Retardant Additives: Their Effect on the
Flammability of Polyureas — Final Report, (DRDC Atlantic CR 2008-048)
Elastochem Specialty Chemicals Inc.
[2] ASTM Standard E1354-08 (2008), Standard Test Method for Heat and Visible Smoke
Release Rates for Materials and Products Using an Oxygen Consumption
Calorimeter. ASTM International, West Conshohocken, PA.
[3] United States of America, Department of Defense (1991), Fire and toxicity test
methods and qualification procedure for composite material systems used in hull,
machinery, and structural applications inside naval submarines. Department of
Defense Test Method Standard. MIL-STD-2031.
[4] Langille, K., Nguyen, D., and Veinot, D. E. (1999), Inorganic Intumescent Coatings
for Improved Fire Protection of GRP, Fire Technology, 35, 99–110.
[5] Levchik, S. (2007), Flame Retardant Polymer Nanocomposites, New York: John
Wiley & Sons.
16 DRDC Atlantic CR 2009-071
Product Information
MONDUR M Aromatic Diisocyanate
Descript ion
Mondur M is a high-purity-grade difunctionalisocyanate, diphenylmethane 4,4’-diisocyanate(MDI), available in three forms: flaked solid, fusedcake, and molten liquid.
Applicat ion
Mondur M diisocyanate can be used in the produc-tion of solid polyurethane elastomers, adhesives,coatings, and in intermediate polyurethane products.As with any product, use of Mondur M in a givenapplication must be tested (including but not limitedto field testing) in advance by the user to determinesuitability.
Product Specificat ions
Flaked Fused Molten
Assay, wt. % (min) 99.5 99.5 99.5
Acidity, (as HCl), % ppm 15 15 15
Color of melt, APHA (max) 200 20 20
MDI Dimer, wt. % 0.7 1.0 0.3
Hydrolyzable chloride,
ppm (max) 20 20 15
Typical Propert ies*
Flaked Fused Molten
Appearance white to colorless colorless
slightly solid liquid
yellow
Specific gravity @ 50C/15.5C 1.19 1.19 1.19
Flash point, PMCC,°C 202 202 202
Viscosity, mPa•s - - 4.1
Bulk density, lb/gal 4.6 - 5.8 10 9.93
Freezing Temperatures, ºC 39 39 39
Storage and Handling
Mondur M isocyanate must be stored in tightlyclosed containers and protected from contaminationwith moisture and foreign substances that canadversely affect processing. Contamination canresult in the formation of solids, the evolution of gas,and/or significant amounts of heat. Mondur Misocyanate will react with water to form ureas andliberate CO
2 gas, which may cause sealed contain-
ers to expand and rupture. Partially filled containersshould be blanketed with dry nitrogen.
Storage Temperatures and Shipping Conta iners
Flaked Fused Molten Bulk
Recommended 5°C 5°C 41-44°C
Storage Temperature (41°F) max** (41°F) max** (107°-111°F)
Storage Time
at Recommended 3 months 3 months 3 weeks
Temperature (max)
Shipping Containers 4-lb pails 1-lb pails Truck trailers
20-lb pails 5-lb pails 1,500-4,500
88-lb drums 55-gal drums gal
Dimer Formation. During storage, Mondur Misocyanate slowly reacts to form self-condensationproducts known as MDI dimer. Dimer is undesirablebecause it is only slightly soluble in the moltenproduct and in time will cause turbidity and/or form asolid precipitate. Dimer formation occurs in bothliquid and solid Mondur M isocyanate, and the rateof dimer formation for both is determined by thestorage temperature. Therefore, storage tempera-ture is the critical factor which determines thestorage life of both solid and liquid Mondur Misocyanate.
Page 1 of 3 — Document contains important information and must be read in its entirety.
* These items are provided as general information only. They are approximate values and are not part of the product specifications.
18 DRDC Atlantic CR 2009-071
To avoid rapid dimer formation, and a significantshortened storage life, Mondur M isocyanate mustnot be allowed to remain at temperatures between20° and 39°C (68° and 122°F). Dimer forms in solidMondur M isocyanate at a very rapid rate somewhatbelow its melting point of 39°C (102°F). If solidMondur M isocyanate is allowed to remain at thistemperature for seveal hours, it can form enoughdimer to become unusable. This can occur, forexample, when a drum or vessel of liquid isocyanateis allowed to slowly freeze due to exposure toambient temperature.
Storage Temperature for Flaked or FusedMondur M Isocyanate. Store fused or flakedMondur M isocyanate at 5°C (41°F) or lower, whichwill provide a storage life of about three months. Attemperatures of -20°C max (-4°F max), flaked orfused Mondur M isocyanate can be stored up to sixmonths. Storage temperatures up to 15°C (59°F) arepossible, if the correspondingly shorter storage life isacceptable. Strictly avoid the storage of solid MondurM isocyanate between 20° and 39°C (68° and102°F) because the formation of dimer is very rapidat these higher temperatures.
Storage Temperature for Molten Mondur MIsocyanate. The recommended temperature rangefor storing molten Mondur M isocyanate is 42° to44°C (107° to 111°F). The reasons for this narrowrange are:
•The freezing point of Mondur M isocyanate is 39°C (103°F) and it will quickly freeze at or below this temperature. Freezing drasti cally promotes the formation of MDI dimer.
•Above 44°C (111°F) the storage life is shortened due to the formation of a solid precipitate of MDI dimer.
Even when properly stored, liquid Mondur M isocy-anate has a limited storage life of only three weeks.The storage life of molten Mondur M isocyanate isshort compared to most other bulk chemicals,requiring good planning and inventory control.
Bayer MaterialScience has extensive experience inthe design and operation of facilities for the storageand handling of molten Mondur M isocyanate. Pleasecontact your Bayer MaterialScience representativefor more information.
Melting Flaked Mondur M Isocyanate. FlakedMondur M isocyanate is especially convenient forsmaller operations, since the flaked material may beeasily transferred to the appropriate vessel withoutprior melting. It is recommended that flaked MondurM isocyanate be melted in heat jacketed vesselsequipped with an agitator. This will ensure rapidmelting and uniform heating with minimum formationof MDI dimer. Proper ventilation must be used whenmelting material.
Melting Fused Mondur M Isocyanate. Melt fusedMondur M isocyanate as quickly as posible – withoutoverheating — to minimize dimer formation. Thepreferred method for melting fused Mondur Misocyanate is to heat it in a steam cabinet whileslowly rolling the drum. This method normally takes 4to 5 hours to melt 55-gallon drums of fused MondurM isocyanate. Uneven heating without rolling willincrease the amount of MDI dimer formation and thetime needed to completely melt the material. If adrum roller is not used, some method of agitationmust be employed to thoroughly homogenize themelted product. Proper ventilation must be usedwhen melting material.
A hot room (60°C to 80°C/140° to 176°F) can alsobe used. The time needed to melt fused Mondur Misocyanate in a hot room depends on temperature,heat source, air circulation and the amount of mate-rial being melted. Times must be determined empiri-cally, based on specific equipment.
When melted, use the entire contents of the con-tainer, if possible. Otherwise, blanket the remainingMondur M isocyanate with nitrogen and store at atemperature of 42° to 44°C (107° to 111°F). Do notattempt to refreeze melted Mondur M isocyanate.
During melting, monitor the drums for abnormalities— particularly swelling — and discontinue heatingshould any be observed. Swollen drums are poten-tially dangerous and must be handled only by trainedpersonnel. Contact Bayer MaterialScience’s ProductSafety Department for guidelines on handling swollendrums. See Material Safety Data Sheet for emer-gency telephone numbers.
If no abnormalities are observed, open the drums ofmelted Mondur M in a well-ventilated area. Appro-priate personal protection equipment must be used(see Material Safety Data Sheet). Remove anymoisture from the top of the drum and open the bungslowly to relieve pressure build-up that may haveoccurred during the melting process.
Page 2 of 3 — Document contains important information and must be read in its entirety.
DRDC Atlantic CR 2009-071 19
If moisture contamination has occurred, do notattempt to melt the product, because the moisturewill react with the isocyanate and result in a danger-ous pressure build-up of carbon dioxide in a closedsystem.
Do not use electric heating devices or any type ofhigh temperature equipment for melting Mondur Misocyanate. High temperatures can cause decompo-sition of the isocyanate and the formation of gaseswhich can build up pressure in closed containers andcause them to rupture, possibly resulting in seriousinjury.
Filtration of Mondur M Isocyanate. It is possible tofilter small amounts of dimer from Mondur Misocyanate. This is typically done when no turbidityor particulates can be tolerated in the process.Contact your Bayer MaterialScience representativefor specific filter equipment recommendations basedon your processing needs.
Filtration cannot solve a dimer problem. WhenMondur M isocyanate has reached the end of itsstorage life — indicated by a significant formation ofsolids — the only really satisfactory solution is torapidly use the remaining product.
Health and Safety Informat ion
Appropriate literature has been assembled whichprovides information pertaining to the health andsafety concerns that must be observed when han-dling Mondur M diisocyanate. For materials men-tioned that are not Bayer products, appropriateindustrial hygiene and other safety precautionsrecommended by their manufacturer should befollowed. Before working with any product men-tioned in this publication, you must read and becomefamiliar with available information concerning itshazards, proper use, and handling. This cannot beoveremphasized. Information is available in severalforms such as material safety data sheets andproduct labels. For further information contact yourBayer MaterialScience representative or the ProductSafety and Regulatory Affairs Department in Pitts-burgh, PA.
Page 3 of 3 — Document contains important information and must be read in its entirety.
Note: The information contained in this bulletin is current as of June 2002. Please contact BayerMaterialScience to determine whether this publication has been revised.
Bayer Materia lScience LLC
100 Bayer Road • Pittsburgh, PA 15205-9741 • Phone: 1-800-662-2927 • www.BayerMaterialScienceNAFTA.com
The manner in which you use and the purpose to which you put and utilize our products, technical assistance and information (whether verbal, written or by
way of production evaluations), including any suggested formulations and recommendations are beyond our control. Therefore, it is imperative that you testour products, technical assistance and information to determine to your own satisfaction whether they are suitable for your intended uses and applications.
This application-specific analysis must at least include testing to determine suitability from a technical as well as health, safety, and environmental
standpoint. Such testing has not necessarily been done by us. Unless we otherwise agree in writing, all products are sold strictly pursuant to the terms ofour standard conditions of sale. All information and technical assistance is given without warranty or guarantee and is subject to change without notice. It is
expressly understood and agreed that you assume and hereby expressly release us from all liability, in tort, contract or otherwise, incurred in connection with
the use of our products, technical assistance, and information. Any statement or recommendation not contained herein is unauthorized and shall not bind us.Nothing herein shall be construed as a recommendation to use any product in conflict with patents covering any material or its use. No license is implied or
in fact granted under the claims of any patent.
Sales Offices
17320 Redhill Avenue, Suite 175, Irvine, CA 92614-5660 • 1-949-833-2351 • Fax: 1-949-752-13061000 Route 9 North, Suite 103, Woodbridge, NJ 07095-1200 • 1-732-726-8988 • Fax: 1-732-726-1672
2401 Walton Boulevard, Auburn Hills, MI 48326-1957 • Phone: 1-248-475-7700 • Fax: 1-248-475-7701
6/02
20 DRDC Atlantic CR 2009-071
GELEST, INC. 11 East Steel Rd. Morrisville, PA 19067
Phone: (215) 547-1015 MATERIAL SAFETY EMERGENCY TELEPHONE DATA SHEET CHEMTREC: 1-800-424-9300 NAME: POLY(DIMETHYLSILOXANE), AMINOPROPYL TERMINATED - DMS-A15
CHEMICAL NAME: POLY(DIMETHYLSILOXANE), AMINOPROPYL TERMINATED SYNONYMS: AMINOPROPYL TERMINATED POLYDIMETHYLSILOXANE CHEMICAL FAMILY: SILICONE HMIS CODES HEALTH: 1 FLAMMABILITY: 1 REACTIVITY: 0
INGREDIENTS
IDENTITY CAS NO. % TLV OSHA PEL POLY(DIMETHYLSILOXANE), AMINOPROPYL TERMINATED 106214-84-0 >95 not established
PHYSICAL DATA
Boiling Point: >205°C Melting Point: <-60°C Specific Gravity: 0.97 Vapor Pressure: not determined Vapor Density, air = 1: NA Solubility in water: insoluble % volatiles: <3 Evaporation rate: NA Molecular Weight: 2500-4000 Viscosity: 40-60 cSt Appearance & Color: Clear liquid
FIRE & EXPLOSION DATA Flash Point, COC: 205°C (400°F) Autoignition Temp.: not determined Flammability Limits- LEL: NA UEL: NA Extinguishing Media: Water spray or fog, foam, carbon dioxide, dry chemical. Special Fire Fighting Procedures: Avoid eye and skin contact. Do not breathe fumes or inhale vapors. Unusual Fire and Explosion Hazards: Irritating fumes and organic acid vapors may develop when material is exposed to elevated temperatures or open flame.
-1-(DMS-A15)
DRDC Atlantic CR 2009-071 21
ENVIRONMENTAL INFORMATION Spill response: Sweep material and transfer to a suitable container for disposal. Recommended Disposal: Incinerate. Follow all chemical pollution control regulations.
HEALTH HAZARD DATA
Eye Contact: May cause immediate or delayed severe eye irritation. Skin contact: No information available. Avoid Contact. Inhalation: No information available. Avoid inhalation. Oral Toxicity: not determined Inhalation Toxicity: not determined SUGGESTED FIRST AID EYES: In case of contact, immediately flush eyes with flowing water for at least 15 minutes. Get medical attention. SKIN: Flush with water, then wash with soap and water. INHALATION: Move exposed individual to fresh air. Administer oxygen if needed. Call a physician. INGESTION: Never give fluids or induce vomiting if patient is unconscious or having convulsions. To conscious individual give one full cup of water to dilute ingested material. Get medical attention.
REACTIVITY DATA Stability: Stable Conditions to avoid: Store away from oxidizers. Hazardous decomposition products: Organic acid vapors and silicon dioxide.
SPECIAL PROTECTION INFORMATION
Ventilation: Local exhaust is recommended. Mechanical is recommended. Respiratory Protection: If exposure exceeds TLV, NIOSH approved organic vapor respirator. Eye and Face Protection: Chemical worker’s goggles. Do not wear contact lenses. Other Clothing and Equipment: Rubber, neoprene or nitrile gloves. An eyewash and emergency shower should be available. Launder clothing before reuse.
-2-(DMS-A15)
22 DRDC Atlantic CR 2009-071
OTHER PRECAUTIONS
For research and industrial use only. Storage and Handling: Store in sealed containers.
TRANSPORTATION
DOT SHIPPING NAME: CHEMICALS, NOI DOT HAZARD CLASS: None required DOT LABEL: None required DOT ID No: None required Prepared by safety and environmental affairs ISSUE DATE DMS-A15: 3/3/03 SUPERSEDES: 7/31/02 The information contained in this document has been gathered from reference materials and/or Gelest, Inc. test data and is to the best knowledge and belief of Gelest, Inc. accurate and reliable. Such
information is offered solely for your consideration, investigation and verification. It is not suggested or guaranteed that the hazard precautions or procedures described are the only ones which exist. Gelest, Inc. makes no warranties, express or implied, with respect to the use of such information and assumes no
responsibility therefore.
-3-(DMS-A15)
DRDC Atlantic CR 2009-071 23
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24 DRDC Atlantic CR 2009-071
Annex B: ACT Labs FTIR Spectra of Base
Polyureas
FTIR spectra for P2P1S1, Exolit OP 560 substituted diisocyanate.
FTIR spectra for P2P1S2, DMS-A15 substituted polyether amine.
””
DRDC Atlantic CR 2009-071 25
FTIR spectra for P2P1S3, Exolit OP 560 substituted diisocyanate and DMS-A15
substituted polyether amine.
26 DRDC Atlantic CR 2009-071
An
nex
C:
In-h
ou
se
Fla
me
Te
stin
g
mic
a(g
)
zin
cb
ora
te(g
)
sod
ium
ph
osp
hate
(g)
Poly
bor
(g)
am
mon
ium
sulf
ate
(g)
sila
zan
e(g
)
talc
(g)
AP
P/t
riis
ocy
an
ura
te3:1
(g)
trea
ted
gra
ph
ite
(g)
ure
a(g
)
zin
cst
eara
te(g
)
am
mon
ium
ph
osp
hate
(g)
AT
H(g
)
trip
hen
ylp
hosp
hate
(g)
sod
ium
bic
arb
on
ate
(g)
AP
P(g
)
zeoli
te(g
)
mel
am
ine
(g)
Init
ial
mass
(g)
Mass
aft
erb
urn
(g)
Mass
loss
(g)
%lo
ss
Ign
itio
nti
me
(s)
Tim
eto
exti
nct
ion
(s)
Ch
ar
typ
e
Bon
ded
3v0 15.3 11.8 3.5 22.9 4 3 liquifies n
3v1 20 27.7 26.1 1.6 5.8 4 30 good y
3v2 20 27.2 25.9 1.3 4.8 5 30 powder n
3v3 20 31.0 30.1 0.9 2.9 n/a 1 spotty y
3v4 20 32.8 32.0 0.8 2.4 7 10 v. good n
3v5 20 35.9 34.9 1.0 2.8 11 3 flakey n
3v6 4 19.6 18.4 1.2 6.1 4 30 flakey y
3v7 20 27.5 26.4 1.1 4.0 4 30 powder n
3v8 20 28.9 28.7 0.2 0.7 n/a 1 excellent y
3v9 20 30.5 30.3 0.2 0.7 8 0 powder n
3v10 20 31.5 28.8 2.7 8.6 12 0 liquifies n
3v11 10 31.0 28.8 2.2 7.1 3 30 liquifies n
3v12 20 31.9 30.8 1.1 3.4 10 1 liquifies n
3v13 20 31.6 30.8 0.8 2.5 7 30 good y
3v14 20 31.8 27.9 3.9 12.3 2 3 liquifies n
3v15 20 30.7 29.5 1.2 3.9 6 3 good y
3v16 10 36.8 36.3 0.5 1.4 7 5 flakey n
3v17 20 32.5 30.9 1.6 4.9 6 30 excellent y
3v18 20 28.9 28.4 0.5 1.7 15 2 good y
Single ingredient trials, base Polyurea Rubinate 9009 + Ethacure 100/300 + D2000, 30 Second Burn at 1100◦F, 50 g sample.
DR
DC
Atla
ntic
CR
20
09
-07
12
7
mic
a(g
)
zin
cb
ora
te(g
)
sod
ium
ph
osp
hate
(g)
Poly
bor
(g)
am
mon
ium
sulf
ate
(g)
sila
zan
e(g
)
talc
(g)
AP
P/t
riis
ocy
an
ura
te3:1
(g)
trea
ted
gra
ph
ite
(g)
ure
a(g
)
zin
cst
eara
te(g
)
am
mon
ium
ph
osp
hate
(g)
AT
H(g
)
trip
hen
ylp
hosp
hate
(g)
sod
ium
bic
arb
on
ate
(g)
AP
P(g
)
zeoli
te(g
)
mel
am
ine
(g)
Init
ial
mass
(g)
Mass
aft
erb
urn
(g)
Mass
loss
(g)
%lo
ss
Ign
itio
nti
me
(s)
Tim
eto
exti
nct
ion
(s)
Ch
ar
typ
e
Bon
ded
3v19 5 5 5 2 32.1 31.2 0.9 2.8 6 27 spotty y
3v20 5 5 5 5 33.0 32.1 0.9 2.7 9 30 spotty y
3v21 5 5 5 5 34.9 34.1 0.8 2.3 5 20 flakey n
3v22 5 5 5 5 32.4 31.5 0.9 2.8 11 2 spotty y
3v23 5 2 5 5 25.8 24.4 1.4 5.4 5 30 excellent y
3v24 5 2 5 5 29.6 28.6 1.0 3.4 9 30 good y
3v25 5 5 2 5 27.4 25.9 1.5 5.5 4 30 good y
3v26 5 5 5 5 29.6 28.5 1.1 3.7 10 30 flakey n
3v27 5 5 2 5 29.1 28.0 1.1 3.8 2 30 excellent n
3v28 5 5 5 2 30.4 30.2 0.2 0.7 n/a 0 ash n
3v29 5 2 5 5 29.7 28.5 1.2 4.0 5 30 good y
3v30 5 5 2 5 30.1 29.5 0.6 2.0 7 11 flakey n
3v31 5 5 5 2 31.2 30.4 0.8 2.6 3 12 flakey n
3v32 5 5 5 5 35.6 34.7 0.9 2.5 11 13 flakey y
3v33 5 5 2 5 30.7 28.7 2.0 6.5 4 30 good n
3v34 5 5 5 5 33.1 32.1 1.0 3.0 28 0 spotty y
3v35 5 5 5 5 29.1 28.2 0.9 3.1 6 19 good n
3v36 5 5 5 5 30.9 30.2 0.7 2.3 10 7 flakey y
First set of combinations, base Polyurea Rubinate 9009 + Ethacure 100/300 + D2000, 30 Second Burn at 1100◦F, 50 g sample.
28
DR
DC
Atla
ntic
CR
20
09
-07
1
sod
ium
ph
osp
hate
(g)
Poly
bor
(g)
am
mon
ium
sulf
ate
(g)
sila
zan
e(g
)
AP
P/t
riis
ocy
an
ura
te3:1
(g)
trea
ted
gra
ph
ite
(g)
ure
a(g
)
am
mon
ium
ph
osp
hate
(g)
sod
ium
bic
arb
on
ate
(g)
AP
P(g
)
zeoli
te(g
)
mel
am
ine
(g)
Init
ial
mass
(g)
Mass
aft
erb
urn
(g)
Mass
loss
(g)
%lo
ss
Ign
itio
nti
me
(s)
Tim
eto
exti
nct
ion
(s)
Ch
ar
typ
e
Bon
ded
3v37 2 2 2 2 2 2 2 2 2 2 2 35.0 34.8 0.2 0.6 n/a 0 strand y
3v38 5 5 5 2 1 2 35.0 34.8 0.2 0.7 n/a 0 strand y
3v39 5 4 4 4 1 2 30.5 30.3 0.2 2.8 n/a 0 strand y
3v40 5 4 4 4 1 2 32.7 31.8 0.9 2.1 10 2 good y
3v41 5 5 4 4 1 2 32.8 32.1 0.7 0.9 13 5 excellent y
3v42 4 3 3 3 3 1 3 32.4 32.1 0.3 2.2 n/a 0 strand y
3v43 4 3 3 3 3 2 1 1 35.6 34.8 0.8 1.0 18 1 good y
3v44 9 1 1 1 1 1 1 1 1 1 1 1 29.6 29.3 0.3 1.9 25 1 strand y
3v45 5 5 5 2 1 2 26.5 26.0 0.5 1.8 16 2 strand y
3v46 13 1 1 1 4 32.5 31.9 0.6 2.2 14 3 good slightly
3v47 5 3 3 3 3 1 2 32.0 31.3 0.7 0.3 26 0.5 good y
3v48 15 2 1 2 34.9 34.8 0.1 2.0 28 0 strand y
3v49 8 8 1 1 1 1 34.8 34.1 0.7 2.6 26 0.5 good y
3v50 7 7 2 1 1 2 34.2 33.3 0.9 2.5 16 2 good y
Second set of combinations, base Polyurea Rubinate 9009 + Ethacure 100/300 + D2000, 30 Second Burn at 1100◦F, 50 g sample.
DR
DC
Atla
ntic
CR
20
09
-07
12
9
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30 DRDC Atlantic CR 2009-071
Distribution list
DRDC Atlantic CR 2009-071
Internal distribution
2 R.S. Underhill: 1CD, 1 hard copy
1 J. Hiltz
1 L.M. Cheng (H/DL(A))
3 DRDC ATLANTIC LIBRARY FILE COPIES
Total internal copies: 7
External distribution
2 Brenda DiLoreto: 1CD, 1 hard copy
Elastochem Specialty Chemicals Inc.
37 Easton Road
Brantford ON N3P 1J4
1 NDHQ/DRDC/DRDKIM 3
1 Library & Archives Canada
Attention: Military Archivist, Government Records Branch
Total external copies: 4
Total copies: 11
DRDC Atlantic CR 2009-071 31
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32 DRDC Atlantic CR 2009-071
DOCUMENT CONTROL DATA
(Security classification of title, body of abstract and indexing annotation must be entered when document is classified)
1. ORIGINATOR (The name and address of the organization preparing the
document. Organizations for whom the document was prepared, e.g. Centre
sponsoring a contractor’s report, or tasking agency, are entered in section 8.)
Elastochem Specialty Chemicals Inc.
37 Easton Road
Brantford ON N3P 1J4
2. SECURITY CLASSIFICATION (Overall security
classification of the document including special
warning terms if applicable.)
UNCLASSIFIED
3. TITLE (The complete document title as indicated on the title page. Its classification should be indicated by the appropriate
abbreviation (S, C or U) in parentheses after the title.)
Investigation of Fire Resistant Polyurea Systems: Final Report
4. AUTHORS (Last name, followed by initials – ranks, titles, etc. not to be used.)
DiLoreto, B.; DiLoreto, S.
5. DATE OF PUBLICATION (Month and year of publication of
document.)
October 2009
6a. NO. OF PAGES (Total
containing information.
Include Annexes,
Appendices, etc.)
44
6b. NO. OF REFS (Total cited
in document.)
5
7. DESCRIPTIVE NOTES (The category of the document, e.g. technical report, technical note or memorandum. If appropriate, enter the type
of report, e.g. interim, progress, summary, annual or final. Give the inclusive dates when a specific reporting period is covered.)
Contract Report
8. SPONSORING ACTIVITY (The name of the department project office or laboratory sponsoring the research and development – include
address.)
Defence R&D Canada – Atlantic
PO Box 1012, Dartmouth NS B2Y 3Z7, Canada
9a. PROJECT OR GRANT NO. (If appropriate, the applicable
research and development project or grant number under which
the document was written. Please specify whether project or
grant.)
11gy05
9b. CONTRACT NO. (If appropriate, the applicable number under
which the document was written.)
W7707-088115/001/HAL
10a. ORIGINATOR’S DOCUMENT NUMBER (The official document
number by which the document is identified by the originating
activity. This number must be unique to this document.)
DRDC Atlantic CR 2009-071
10b. OTHER DOCUMENT NO(s). (Any other numbers which may be
assigned this document either by the originator or by the
sponsor.)
11. DOCUMENT AVAILABILITY (Any limitations on further dissemination of the document, other than those imposed by security classification.)
( X ) Unlimited distribution
( ) Defence departments and defence contractors; further distribution only as approved
( ) Defence departments and Canadian defence contractors; further distribution only as approved
( ) Government departments and agencies; further distribution only as approved
( ) Defence departments; further distribution only as approved
( ) Other (please specify):
12. DOCUMENT ANNOUNCEMENT (Any limitation to the bibliographic announcement of this document. This will normally correspond to the
Document Availability (11). However, where further distribution (beyond the audience specified in (11)) is possible, a wider announcement
audience may be selected.)
unlimited
13. ABSTRACT (A brief and factual summary of the document. It may also appear elsewhere in the body of the document itself. It is highly desirable
that the abstract of classified documents be unclassified. Each paragraph of the abstract shall begin with an indication of the security
classification of the information in the paragraph (unless the document itself is unclassified) represented as (S), (C), or (U). It is not necessary to
include here abstracts in both official languages unless the text is bilingual.)
DRDC Atlantic is interested in evaluating polyurea coatings for use in enclosed spaces as damage
control materials. For such applications, their fire resistant properties need to be improved. The work
reported here is divided into two parts. In Part 1, three base polyurea formulations were developed
and evaluated by cone calorimetry. The goal was to replace portions of the organic polyurea backbone
to improve the flame retardancy. The first sample utilized an diisocyanate prepolymer with a portion of
its backbone made up of a phosphorous polyol, the second sample replaced a portion of the polyether
amine with an amine terminated polydimethylsiloxane and the third sample combined the phosphorous
polyol with the amine terminated polydimethylsiloxane. Cone calorimetry determined that the third
sample yielded the best results for lowering smoke production and increasing time to ignition. It is
believed that the phosphorous polyol and polydimethylsiloxane have a synergistic effect in improving
the flame properties.
In Part 2 of this work, the phosphorous polyol/ polydimethylsiloxane based polyurea was used as
the base formulation and various combinations of flame retardant additives were incorporated in an
attempt to further improve the flame properties. Cone calorimetry indicated that the best combinations
included sodium phosphate, ammonium polyphosphate (APP)/triisocyanurate 3:1, treated graphite,
urea, zeolite and melamine.
14. KEYWORDS, DESCRIPTORS or IDENTIFIERS (Technically meaningful terms or short phrases that characterize a document and could be
helpful in cataloguing the document. They should be selected so that no security classification is required. Identifiers, such as equipment model
designation, trade name, military project code name, geographic location may also be included. If possible keywords should be selected from a
published thesaurus. e.g. Thesaurus of Engineering and Scientific Terms (TEST) and that thesaurus identified. If it is not possible to select
indexing terms which are Unclassified, the classification of each should be indicated as with the title.)
fire safe materials, fire retardant materials, char, polymer, polymer degradation, polymer decomposi-
tion, polyurea
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