Novel Surfactant Technology to Improve Polyurethane Spray

Performance



Christian Eilbracht, Carsten Schiller
Degussa AG
Goldschmidt Polyurethane Additives
Goldschmidtstrasse 100
45127 Essen, Germany
Peter Hohl
Degussa AG
Goldschmidt Polyurethane Additives
Goldschmidt Chemical Corp.
914 East Randolph Road
Hopewell, VA 23860


ABSTRACT

Spray Polyurethane foam is a versatile construction product that can be easily applied to multiple types of surfaces with
multiple types of contours. Due to this versatility, it has quickly become the product of choice for insulating new buildings
and upgrading existing structures, both interior walls and existing roofs. Its ability to control both air and moisture
penetration, while still providing high levels of R-value are truly unique when one considers its ease of application.
The broad range of spray foam applications are rooted in the great versatility of the polyurethane chemistry.
Formulations can be modified in order to achieve a desired set of final foam performance criteria. Recent changes in
blowing agent technologies (HFCs - 245fa and 365mfc/227 blends, hydrocarbons and all water), polyol technologies
(petroleum-based vs. vegetable based) and flame retardant technology have all had a great impact on how todays
formulators practice their art.
This paper will discuss the growing role that surfactant technology plays in these next-generation spray systems. A
series of experiments have been designed to illustrate how tailor made surfactants can improve foam quality and provide
better blowing agent utilization. The resulting data clearly demonstrates how utilizing the correct surfactant molecule can
provide solutions to a great range of challenges experienced by todays formulators. Tailor made surfactants are a powerful
tool in helping to meet the spray polyurethane foam manufacturers ongoing demand for balancing foam performance with
lowest cost-in-use production.

INTRODUCTION

The Global market for polyurethane products is diverse and complex with a myriad of end-users. It has been growing at
an average rate of over seven percent per annum for the last 15 years. The growth of polyurethane construction market
segment has mainly been driven in the past 10 years by the penetration of polyurethanes into new construction fields.[1]
One of the fastest growing segments is spray polyurethane foam, in particular, those systems designed for wall insulation.
Spray polyurethane for wall applications has become popular for both its insulation and air barrier characteristics. Like
other rigid polyurethane, the two main types of wall spray systems; 0.5 and 2.0 lb/ft
3
, are the result of a reaction between a
resin blend, containing some combination of polyol, blowing agent (chemical and/or physical), catalyst, surfactant and
methylene diphenyl diisocyanate (MDI). What makes these systems different from the more traditional types of
polyurethane foam is that they are not manufactured in a controlled industrial environment such as metal panels or
boardstock, but the foam is sprayed at a the construction job site. Due to the wide range in variables that can be encountered
at a job site (temperature and humidity) formulators are required to develop formulations that not only produce good final
foam physical properties (i.e. yield, adhesions, thermal properties) but also that are robust enough to perform in the field
under non-optimal conditions.[2,3,4]
It has been shown in past work that surfactants play an integral part in the performance of polyurethane foam, both in the
final performance as well as increasing a systems processing latitude. This has been found to be true for both flexible and
rigid polyurethane foam applications, for both low and high density foam applications, for both fast and slow reacting
systems and for all the various combinations of physical and chemical blowing agent to date.[5,6,7,8] It is in light of this
historical perspective that Degussa Goldschmidt has looked to understand how significant an impact tailor made surfactants
can have on the performance of these types of wall insulation foams, both 0.5 and 2.0 pcf systems. This paper will discus
results from a series of experiments that were designed to quantify the surfactant structure influence on three different wall
spray formulations

EXPERIMENTAL

Spray Polyurethane foam can be considered unique when compared to traditional rigid foam applications. Due to its fast
reactivity and distinctive processing, it became apparent that the underlining goal of this paper was to try and determine
some of the fundamental structural characteristics of surfactant technology that have the greatest influence on those
characteristics that are most important to the spray polyurethane foam market.
Based on this premise, a series of experiments were conducted that looked to quantify the impact that surfactants can have
on both 0.5 and 2.0 pcf wall spray systems. For this reason, three separate wall spray formulation were investigated. A
nominal 2.0 pcf system (utilizing HFC 245fa), a 0.5 pcf system (all water) and a 0.5 pcf system (all water) that contains 25%
renewable polyol source. To develop a baseline for this work, handmix studies were completed using Degussa
Goldschmidts established stimulus-response techniques to identify surfactant structures that showed desirable foam
characteristics in all three systems. [9] As expected, due to the base formulation differences all three systems identified
multiple surfactant structures that warranted further investigation.
Due to the basic research nature of this study and the desire to better understand the surfactant structure foam
performance relationship, all surfactants in this study were specifically designed to test specific structure performance
relationships within the parameters of each of the three spray formulations. Finally, as the systems were further
investigated, a total of 21 experimental surfactants were screened on a Graco proportioning spray unit.
All samples were sprayed onto a large sheet of drywall in a single pass. The resulting foams were tested for:

The Surfactants Effect on:
Improved Yield (Average Density)
Achieving dimensional stability
Maximizing K-factor value (in the case of 2.0 pcf foam)
Maximizing adhesion
Positively effecting resulting flame and smoke numbers
Ease of handling (spray pattern, edge)

Physical Testing Methods

All samples were cured at least 24 hours before testing began.
Average Density Calculation
The average of five core samples, at various locations, were taken, measured and recorded for each
individual surfactant evaluation.
Dimensional Stability Determination
Samples were aged in a humidity cabinet at 158
o
F and ~95% relative humidity for 72 hours.
Thermal Conductivity Determination
To determine the thermal conductivity of the produced foams, three test samples were cut from the
resulting sprayed panel. A Fox 300 Laser Comp was then used to measure the resulting thermal
properties. The data shown in the tables are the average of the three samples.
Flame Spread and Smoke Generation Determination
A series of burn testes were completed in a research tunnel developed and operated by the West
Development Group, located in LaGrange Ohio. This research burn tunnel is essentially a scaled down
version of the Steiner Tunnel (ASTM E-84) test. The maximum flame spread and smoke index results
have been demonstrated, through multiple testing, to correlate very well to E-84 results at UL.

RESULTS AND DISCUSSIONS

Section 1: Surfactant Influence on 2.0 pcf Wall Spray System

The intent of this experiment was to generate a generic formulation (see Table 1) that met the basic requirements of a
commercially viable 2.0 pcf spray system using pentaflouropropane (HFC 245fa) as the main blowing agent. The spray
portion of this experiment was conducted by the West Development Group. By employing expert applicators under a
controlled environment, it is believed that an acceptable amount of consistency was achieved to give the following spray
foam results validity (see Table 3).
As the goal of this paper was not to develop the best in class formulation, the results presented in Table 3 should be
viewed solely in the context of the base formulation and to what extent a simple change in surfactant affected the resulting
processing and final foam properties.

Table 1. System A: 2.0 pcf Wall Spray Formulation.
Formulation % Process Conditions
Polyester Polyol 40.0 Spray Unit Graco E-20
Manni ch Based Polyether Polyol 20.0 Spray Gun Fusion
Sucrose Initiated Polyether Polyol 5.0
Flame Retardants 17.0 Pressures (psi)
Catalysts 4.5 A-Side 1300 - 1450
Surfactants 0.5 B-Side 1300 - 1450
Water 2.0
HFC 245fa 11.0 Temperature (
o
F)
A-Side Hose 120
B-Side Hose 120

On reviewing the results presented in Table 3, a few very interesting effects are immediately observed. The first is a
general observation. It is evident that even at relatively fast reaction rates, surfactants still significantly impact the resulting
foam thermal conductivity. It had originally been theorized that, assuming reasonable foam was produced, at extremely fast
gelling times the impact of a surfactant on cell nucleation and stabilization of the growing cells would be greatly
marginalized. On inspection of results for samples A5 versus A1 or A8 one can see that this is not the case. One interesting
aspect here is that all foams tested in this experiment, regardless of surfactant, had a high closed cell content. As mentioned
earlier it is believed that the overall fast reactivity of the system is the major driver here but it was also assumed that closed
cell count and K-factor would run more in parallel, i.e. high closed cell content equals the best K-factor. Under further
investigation (see Table 5), it can be noted that those foams that gave good K-factor are also those, not surprisingly, that
have the smallest and most uniform cell structure and not necessarily a higher closed cell content.
A second important aspect worth noting is a surfactants effect of foam yield - - at least as one can relate it to average
density. A simple calculation quickly reveals that a delta of ~8% can be seen between the surfactant with the lowest spray
density (Surfactant A5) and that of the highest density (surfactant A1).
The most surprising of all is the cumulative effect that the surfactant has on both the flame spread and smoke properties of
the resulting sprayed foam. The fact that one could potentially achieve (Surfactant A4) or fail (Surfactant A3 or A5) a class
1 rating in the ASTM E84 trial with a simple surfactant change - while all other physical properties appear to be
equivalent - - clearly illustrates the significant influence that surface active compounds like surfactants have on optimizing a
spray systems performance. More burn evaluations are already underway to better understand this phenomenon.
Finally, the initial spray data (Tables 4 and 5) does appear to indicate that surfactant choice does influence polyurethane
substrate adhesion. Unfortunately at current time, only qualitative results can commented on.

Table 2. System A Surfactants
Surfactant A1 A2 A3 A4 A5 A6 A7
A8
Cloud Point High High High High Medi um Medium Low n.a.
Si l i cone Content High Medi um Medi um Low High Low Low High
Mol ecular Weight Low Medi um Low Low Medi um High Medi um High

Table 3. System A: 2.0 pcf Wall Spray Formulation. - - Results
Surfactant A1 A2 A3 A4 A5 A6 A7 A8
Reactivity (sec)
Cream 2 2 2 2 2 2 2 2
End of Rise 12 12 12 11 12 12 11 13

Average Core Density (pcf) 2.03 1.99 1.98 1.97 1.88 1.92 1.90 1.96

Aged K-Factor 0.1677 0.1563 0.1563 0.1545 0.1523 0.1527 0.1543 0.1855

Open Cel l Content (%) 13 14 12 14 18 12 13 11

Dimensional Stabi l i ty @ < 3 < 4 < 3 < 13 < 4 < 3 < 3 < 3
72 hrs (% change)

Texture Coarse Coarse Coarse Coarse Minor Mi nor Coarse Smooth
Coarse Coarse

Edge Good Orange Orange Orange Good Good Very Good
Peel Peel Peel Good

Spray Pattern Good Good Good Good Good Hard to Very Good
Handle Good

Max Flame Spread 42 44 42 32 42 42 44 40
Smoke Index 549 500 539 365 824 547 582 845





Table 4. System A: 2.0 pcf Wall Spray Formulation. - -Surface Texture
A4
A7 A6
A5
A1
A3
A2
A8
A4 A4
A7 A7 A6 A6
A5 A5
A1 A1
A3 A3
A2 A2
A8 A8


Table 4. System A: 2.0 pcf Wall Spray Formulation. - - Cell Structure
A1 A2 A3
A5 A6 A7
A4
A8
A1 A2 A3
A5 A6 A7
A4
A8


Section 2: Surfactant Influence on 0.5 pcf Wall Spray System

Due to the unanticipated results found when investigating the 2.0 pcf wall spray system, it was decided to further
investigate a surfactants effect on the even more unique 0.5 pcf system. As with the previously discussed 2.0 pcf spray
foam system, the intent in these set of experiments was to generate a generic formulation (see Table 6) that met the basic
requirements of a commercially viable 0.5 pcf spray system, were water was used as the sole chemical blowing agent. The
spray portion of this experiment was again conducted by the West Development Group (WDG) located in LaGrange, Ohio.
Once more by employing expert applicators under a controlled environment, it is believed that an acceptable amount of
consistency was achieved to give the following spray foam results validity (see Table 8).
As the goal of this paper was not to develop the best in class formulation, the results presented in Table 8 should be
viewed solely in the context of the base formulation and to what extent a simple change in surfactant affected the resulting
processing and final foam properties.

Table 6. System B: 0.5 pcf Wall Spray Formulation.
Formulation % Process Conditions
Polyester Polyol 25.0 Spray Unit Graco E-20
Manni ch Based Polyether Polyol 10.0 Spray Gun Fusion
Sucrose Initiated Polyether Polyol 5.0
Flame Retardants 30.0 Pressures (psi)
Catalysts 8.5 A-Side 1450 - 1550
Surfactants 2.5 B-Side 1450 - 1550
Water 19.0
Temperature (
o
F)
A-Side Hose 135
B-Side Hose 135

Results found in tables 8, 9 and 10 clearly highlight those surfactants that achieve acceptable yield (Surfactants B1, B4
and B5) versus those that do not perform well (Surfactants B2, B3 and B6). But of equal importance, from the stance of the
developer, is that two other results, or process performance, seem to go hand-in-hand with achieving that targeted density.
They are the surface texture and spray pattern. It is important to note that when reviewing Table 8 along with the images in
Table 9 and Table 10, it becomes very apparent that, because by the nature of being all water blown and forced to gel in a
very short period of time, these systems are under the regime of strong chemical and physical stress. Stressed to remain
compatible, stressed to expand under such a severe catalytic environment and stressed to be applied by spraying. All these
conditions can be to a great extent managed by employing a surface active component, i.e. the surfactant, that aids in the
emulsification of incompatible raw materials and that can stabilize the rapidly expanding polymer cell structure.

Table 7. System B Surfactants
Surfactant B1 B2 B3 B4 B5 B6
Cloud Point Medi um Medi um High Low n.a.
Low
Si l i cone Content Low High Medium High n.a.
Low
Mol ecular Weight High Medi um High High High
High












Table 9. System B: 0.5 pcf Wall Spray Formulation - - Results
Surfactant B1 B2 B3 B4 B5
B6
Reactivity (sec)
Cream 4 4 4 5 4 4
End of Rise 13 13 13 13 13 11

Average Core Density (pcf) 0.69 1.49 1.17 0.70 0.56 1.16

Open Cel l Content (%) 96 93 96 94 94 90

Dimensional Stabi l i ty @ < 5 < 4 < 5 < 5 < 3 < 3
72 hrs (% change)

Texture Mi nor Popcorn Large Minor Excel l ent Large
Popcorn Popcorn Irregularities Popcorn

Edge Good Bl istering Good Excel l ent Good Heavy

Spray Pattern Excel l ent Good Good Excel l ent Excel l ent Good


Max Flame Spread 42 42 36 42 42 36
Smoke Index 517 434 588 620 484 557

Table 10. System B: 0.5 pcf Wall Spray Formulation - - Surface Texture
B3
B5 B4
B1 B2
B6
B3 B3
B5 B5 B4 B4
B1 B1 B2 B2
B6 B6



Table 11. System B: 0.5 pcf Wall Spray Formulation - - Cell Structure
B3
B5 B4
B1 B2
B6
B3
B5 B4
B1 B2
B6


Section 3: Surfactant Influence on 0.5 pcf Wall Spray System Employing a Renewable Polyol

In order to better understand a surfactants influence on next generation wall spray formulations it was necessary to
investigate renewable polyol technologies. Due to the increased interest in renewable polyol resources in 0.5 pcf spray
systems it was decided to again target a commercially acceptable 0.5 pcf system that would replaced 25% of its polyol with
that of a renewable source. As with the previously discussed 0.5 pcf spray foam system, the intent in these set of
experiments was to create a formulation (see Table 11) that met the basic requirements of a commercially viable 0.5 pcf
spray system, were water was used as the sole chemical blowing agent. The spray portion of this experiment was again
conducted by the West Development Group (WDG) located in LaGrange, Ohio. Once more by employing expert
applicators under a controlled environment, it is believed that an acceptable amount of consistency was achieved to give the
following spray foam results validity (see Table 13).
As stated previously, the goal of this paper was not to develop the best in class formulation, the results presented in
Table 13, 14 and 15 should be viewed solely in the context of the base formulation and to what extent a simple change in
surfactant affected the resulting processing and final foam properties.

Table 12. System C: 0.5 pcf Wall Spray Formulation with Renewable Polyol Technology
Formulation % Process Conditions
Renewable-type Polyol 25.0
Polyester Polyol 7.5 Spray Unit Graco E-20
Manni ch Based Polyether Polyol 7.0 Spray Gun Fusion
Flame Retardants 30.0 Pressures (psi)
Catalysts 8.5 A-Side 1450 - 1550
Surfactants 3.0 B-Side 1450 - 1550
Water 19.0
Temperature (
o
F)
A-Side Hose 135
B-Side Hose 135

A review of the results from Tables 13, 14 and 15 reveal that, similar to what was observed when reviewing the data from
the more traditional 0.5 pcf system (Formulation B), surfactants do indeed play a major role in the foam performance. In
particularly, foam yield and the surface texture of the resulting foam are areas that one can see macro changes in
performance with just small changes in surfactant structures. Reviewing the data more thoroughly, Table 13 clearly
identifies that only four of the seven surfactants achieve even remotely acceptable polymer yield (Surfactants C1, C2, C4
and C7). And unlike the previous 0.5 pcf formulation, those surfactants that performed poorly (C3 and C5) performed very
poorly. That is they produced foams that were showed significant signs of localized cell and foam collapse. At the time of
this paper it is not understood if the use of a renewable polyol was the major factor in causing this failure or just one part of
the puzzle.
Finally, one further observation should be commented on here. It appears that Formulation 3 is much more sensitive, with
respect to surfactant choice, in terms of smoke index. The values, ranging from a low of 548 to a high of 1159, produce a
delta much greater than seen with either of the two systems (Formulation A and B) tested previously. One would naturally
assume that by reviewing the flame spread and chare results would indicate that some foam samples burned hotter and
longer than others thus producing a reasonable correlation between flame spread and smoke generation. Unfortunately this
does not appear to be true in this formulation. Further investigations are planned to better understand this phenomenon.


Table 13. System C: 0.5 pcf Wall Spray Formulation with Renewable Polyol Technology - - Results
Surfactant B1 B2 B3 B4 B5 B6 B7
Reactivity (sec)
Cream 4 4 4 4 4 3 4
End of Rise 10 9 8 9 17 9 9

Average Core Density (pcf) 0.67 0.60 2.27 0.64 1.75 0.97 0.78

Open Cel l Content (%) 94 97 88 98 94 94 97

Dimensional Stabi l i ty @ < 4 < 4 < 1 < 5 < 2 < 4 < 5
72 hrs (% change)

Texture Popcorn Popcorn Minor Excel l ent Good Heavy Good
I rregularities Popcorn

Edge Good Good Poor Excel l ent Poor Heavy Good
Yield Yiel d Popcorn

Spray Pattern Good Good Good Good Good Good Good

Max Flame Spread 42 40 46 40 54 36 44
Smoke Index 1159 654 964 548 758 874 653









Table 14. System C: 0.5 pcf Wall Spray Formulation with Renewable Polyol Technology - - Surface Texture
C1
C2
C3
C4 C5 C6 C7
C1
C2
C3
C4 C5 C6 C7


Table 15. System C: 0.5 pcf Wall Spray Formulation with Renewable Polyol Technology - - Cell Structure
C1
C2
C3
C4
C5 C6 C7
C1
C2
C3
C4
C5 C6 C7



CONCLUSION

The original premise of this paper was to determine to what extent, if any, surfactants have on the performance of spray
formulations. Through a series of formulations, it is clear that surfactants do play a major role in optimizing formulations.
In the 2.0 pcf wall system, the major impact was both K-factor and burn properties. The significance of surfactant on flame
spread and smoke generation is very amazing when one considers that only ~0.25% of surfactant could have such an impact.
Summarizing the results from the 0.5 pcf systems also is quit revealing. It appears that surfactant technology has even a
greater influence on these types of stressed system, in particular on foam yield. It also has become evident that one
surfactant structure does not work for all 0.5 pcf systems, and that tailored solutions are the key to successfully produce the
desired product.
Finally, as this market is expected to continue to grow, as more stringent legislation will come into effect both in the
European Union and the United States regarding building efficiency, formulators will be pressed more and more to achieve
improved foam quality and increase the process window for the contractor. In light of these technical challenges, it will
become even more critical for todays formulators to optimize their spray foam systems. Consequently, it is clear through
this work that the use of a tailored surfactant, specifically designed to optimize the chemical and physical environment of an
individual spray system, will play an integral part in meeting the needs of tomorrows spray polyurethane foam formulations.


REFERENCES

1. Ducker Research Company, Inc. June, 2006. End-use Market Survey on the polyurethane Industry.
2. Bogdan, M., West, D., Blank, w., and Mirasol, s., Impact of Equipment Selection and Environmental Conditions
on Enovate 3000 Blowing Agent Spray Foam. Proceedings of the Polyurethane Expo. 2004.
3. Bogdan, M., Williams, D., Meeting the Needs of the Future with HFC-245fa and HFC-245fa Blend Technology in
the Construction Industry, Proceedings of the Polyurethane Expo. 2001.
4. Goto, J., Sasaki, S., Mashiko, Y., Kambara and Ohki, I., Development of All Water Blown Polyurethane Rigid
Foam for Housing Insulations. Proceedings of the Polyurethanes World Congress, 1997.
5. Eilbracht C., Schiller C., Hohl P. Often Overlooked Factors in PIR Surfactant Development, Proceedings of the
Polyurethanes Expo. 2006.
6. Burkhart, G., M. Klincke, Willoughby K., 2001, Do the Existing Silicone Surfactants Match the Requirements of
HFC-245fa-Blown Appliance Systems?, Proceedings of the Polyurethanes Expo, 2001.
7. Burkhart G.; Klincke M.; Willoughby. K., Optimized Silicone Surfactants for HCFC and Pentane Blown
Polyisocynurate and Polyurethane Rigid Foams, Proceedings of the Polyurethanes Expo. 1995.
8. Burkhart, G., Weier, A., Klincke, M., New, Highly Efficient Silicone Surfactants for Low Density, Water Blown
Rigid Polyurethane Foams. Proceedings of the Polyurethanes World Congress, 1997
9. Eilbracht C., Hohl P. Tailored Surfactantant Solutions to Optimize Foam Performance in HFC-245fa Blown
Appliance Systems, Proceedings of the Polyurethanes Expo. 2004





















BIOGRAPHIES

Christian Eilbracht
Dr. Christian Eilbracht received his Ph.D. in Chemistry with an emphasis on solid state
chemistry at the University of Dortmund in 1997. He then worked for the Clariant Pigment
and Additive Division and was in charge of the R&D activities on flame retardants for flexible
polyurethane foams. He joined the Degussa Goldschmidt PU Additive business line in 2001.
He is currently the global technical director of this polyurethane Business Line within
Degussa.






Carsten Schiller
Dr. Carsten Schiller received his Ph.D. in Chemistry at the University of Bochum with a thesis
on biomaterials for bone substitution in 2003. He changed to the University of Essen and
continued his research activities in the department of Inorganic Chemistry. Since the beginning
of 2005 he joined Degussa Goldschmidt Polyurethane Additives and is currently responsible
for development of additives for rigid foam applications.







Peter Hohl
Mr. Hohl received a BS in Chemistry from Gettysburg College and a MS in Polymer Science
and Engineering from Lehigh University. He joined Air Products and Chemicals in 1993 and
gained invaluable experience working in the field of polyurethane additives development. In
2002, he joined Degussa Goldschmidt Polyurethane Additives and is currently the North
American group leader supporting rigid foam applications.