Materials Today Physics 10 (2019) 100127

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Materials Today Physics

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materials-today-physics

Selection of polymers with functional groups for daytime radiative

cooling
A. Aili a, Z.Y. Wei b, Y.Z. Chen a, D.L. Zhao a, R.G. Yang a, b, *, X.B. Yin a, b, **
a
Department of Mechanical Engineering, University of Colorado, Boulder, CO 80309, United States
b
Materials Science and Engineering Program, University of Colorado, Boulder, CO 80309, United States

a r t i c l e i n f o a b s t r a c t

Article history: The infrared ‘fingerprint’ of polymers that many functional groups/bonds such as CeF and CeO emit
Received 20 May 2019 overlaps with the atmospheric transmittance window and is responsible for the radiative cooling
Received in revised form property of polymers. In this work, we aim to select common polymers applicable to daytime radiative
20 June 2019
cooling by studying the emission/absorption peaks of functional groups in the atmospheric trans-
Accepted 8 July 2019
Available online 17 July 2019
mittance window. We demonstrate week-long subambient radiative cooling of water with two common
polymersdpolyvinylidene fluoride (PVDF) and poly(methyl methacrylate) (PMMA) filmsdby simply
placing them on a silver mirror layer. Although both films have the same thickness of 50 mm, the PVDF
Keywords:
Infrared emission
film has lower solar absorptivity, higher atmospheric window emissivity, and slightly higher selectivity.
Subambient cooling Consequently, its daytime and nighttime cooling performances are both better than those of the PMMA
Water cooling film, with peak sun-hour subambient cooling degrees being 6
C vs. 4
C and peak nighttime subambient
Passive cooling cooling degrees being 9
C vs. 8
C. If used in large-scale cooling systems, such a nuance in cooling
Atmospheric window performance of polymers could lead to a significant economic difference over the long term.
© 2019 Elsevier Ltd. All rights reserved.

Daytime radiative sky cooling is a passive cooling process in developed in the early days were expensive nanophotonic struc-
which a selectively reflective and emissive surface reflects most of tures, which are not suitable for large-scale production in a cost-
the sunlight (with wavelengths 0.3e2.5 mm) and simultaneously effective manner [4e7]. Recently, polymer-based radiative cooling
transfers heat in the form of infrared radiation to the cold universe films and paints are gaining increasing interest owing to their po-
through the atmospheric transparent window (mainly 8e13 mm) tential in mass production, low cost, and applicability to large
[1]. It has been a focus of extensive research studies over the past systems [8,9,11e14]. However, less attention is given to the origin of
few years owing to worldwide initiatives to develop green cooling thermal emission in polymers and their selection. Therefore, un-
technologies that have a low carbon footprint, are energy efficient, derstanding the relationship between the functional groups of
and consume less water. Some earlier studies have shown that both polymers and their mechanisms of infrared thermal emission and
a black emitter and a wavelength-selective emitter over the at- solar absorption may greatly widen the choices of polymers suit-
mospheric window can achieve subambient nighttime radiative able for daytime radiative cooling applications.
cooling [2,3]. However, cooling to subambient temperatures under It is well understood that the vibrations of functional groups are
direct sunlight was achieved only recently, thanks to advancements responsible for infrared absorption and emission by polymers [15].
in nanophotonics and metamaterials that can strongly reflect Different functional groups, such as OeH, C¼O, and CeCl, have
sunlight during the day while maximizing the emissivity over the rather specific vibrational frequencies (wavelengths), although
atmospheric window [4e10]. Daytime radiative cooling surfaces these frequencies may slightly vary depending on the polymer that
hosts the functional groups. Moreover, various vibration modes,
such as stretching and bending vibrations, of an individual func-
tional group generally have different frequencies. As a result, a
* Corresponding author. Department of Mechanical Engineering, University of
Colorado, Boulder, CO 80309, United States.
single type of polymer with several functional groups most likely
** Corresponding author. Department of Mechanical Engineering, University of has many vibrational frequencies. Fig. 1 summarizes the vibration
Colorado, Boulder, CO 80309, United States. modes of functional groups and vibrations regions in polymers in
E-mail addresses: [email protected] (R.G. Yang), Xiaobo.Yin@ terms of frequency and wavelength. As illustrated in Fig. 1a and b, it
colorado.edu (X.B. Yin).

https://doi.org/10.1016/j.mtphys.2019.100127
2542-5293/© 2019 Elsevier Ltd. All rights reserved.
2 A. Aili et al. / Materials Today Physics 10 (2019) 100127

Fig. 1. Vibration modes and vibration regions of functional groups in polymers. (a) Stretching vibration mode, including symmetric and asymmetric stretching vibrations. (b)
Bending vibration mode, including in-plane rocking and scissoring bending vibrations as well as out-of-plane wagging and twisting bending vibrations. (c) Vibration regions in
polymers, including XeH stretching vibration, where X represents C, O, N, and so on, the triple-bond region, where the triple bind is C ≡ C, C ≡ N, and so on, the fingerprint or
crowded region, and the skeletal vibration region.

is possible for a single functional group to have several vibration the atmosphere, while the atmosphere itself also emits very less in
modes such as symmetric and asymmetric stretching vibrations, this region. At the far end of the infrared spectrum is the skeletal
in-plane rocking and scissoring bending vibrations, as well as out- vibration region, where the vibrations of heavy atoms and mole-
of-plane wagging and twisting vibrations. The variety of functional cules, rather than the individual functional group mentioned pre-
groups, together with their various vibration modes, results in a viously, are responsible for the infrared absorption and emission.
large number of infrared abortion/emission peaks in polymers. The previously described vibration regions and the corresponding
The vibration modes over a broad range of wave numbers functional groups are listed in Table 1. The desired functional
(4000e400 cm1) or wavelengths (2.5e25 mm) may be divided into groups, CeO, CeCl, CeF, and CeN, in the fingerprint region may be
several regions. At the larger wave number end, 4000e2500 cm1 used to identify possible polymer candidates for daytime radiative
or 2.5e4 mm, of the spectrum is the XeH (where X represents C, O, cooling. Further selection is required based on solar absorbance,
N, and so on) stretching vibration region in which functional groups manufacturability, physical and chemical stability, durability, and
such as CeH, OeH, and NeH are mainly responsible for emission targeted applications.
and absorption. The high stretching vibrational frequency results As explained earlier, the crowded region, where many func-
from the small mass and volume of these functional groups. tional groups exhibit strong absorption/emission, fully covers the
Following the XeH stretching vibration region is the triple-bond atmospheric window, that is, the infrared thermal radiation is
region, 2500e2000 cm1 or 2.5e4 mm, where functional groups transmitted with negligible absorption by the atmosphere. Based
of C ≡ C and C ≡ N have relatively strong absorptivity because of on this understanding, various polymers are potential choices for
their large force constants [16], although their stretching vibration daytime subambient radiative cooling, provided that these poly-
is weak. In the mid wave number range, 2000-1500 cm1 or mers are highly reflective, highly transparent, or non-absorbing
4e6.7 mm, double-bond functional groups such as C¼C and C¼O over the solar spectrum.
have higher absorptivity owing to stretching vibration. The Here, we report subambient cooling of water by using silver-
fingerprint region, also known as the crowded region, is located backed common polymers, with functional groups from the
further down for the range in 1500e600 cm1 or 6.7e16.7 mm [17]. fingerprint region listed in Table 1. We selected PMMA and PVDF
In this fingerprint or crowded region, many functional groups, films as radiative cooling surfaces. Visually, PMMA is transparent,
including those mentioned previously, and CeY groups, where Y whereas PVDF is semitransparent. As evidenced by the attenuated
represents halogen elements such as F, Cl, and Br, have strong ab- total reflectance Fourier transform infrared spectroscopy spectra of
sorption owing to bending vibrations. Because it is possible that a the films shown in Fig. 2a, PMMA has CeH, C¼O, and CeO groups,
single functional group can have four types of bending vibration and PVDF has CeH and CeF groups, all of which have bending vi-
modes, only a few functional groups in a polymer could produce brations in the crowded region, that is, the atmospheric window.
many absorption peaks. An interesting coincidence here is that the The solar absorptivity and infrared emissivity of the films backed
crowded region, corresponding to 6.7e16.7 mm of the electro- with a silver mirror layer were then measured using UVeVis
magnetic spectrum, covers the entire atmosphere window spectroscopy and infrared spectroscopy in the reflectance mode,
(8e13 mm). The significance of this coincidence is that most of the respectively.
8e13-mm infrared emission from a large number of polymers can Fig. 2b shows the zero-zenith-angle absorptivity/emissivity of
be directly delivered to the deep space without being absorbed by the silver-backed PVDF, PMMA, and blend films over the solar
 A. Aili et al. / Materials Today Physics 10 (2019) 100127 3

Table 1
Vibration regions of functional groups in polymers.

Vibration region Functional groups Dominant group

XeH stretching region (4000e2500 cm1) CeH, OeH, NeH NeH

Triple-bond region (2500e2000 cm1) C ≡ N, C ≡ C C≡N
Double-bond region (2000e1500 cm-1) C¼C, C¼O, C¼N C¼O
Fingerprint region (crowded region, mainly bending vibration) (1500e600 cm-1) CeH, CeO, CeN, Weak but significant overlapping
CeCl, CeF
Skeletal vibration region (600e400þþcm1) Heavy atoms and molecules

Fig. 2. Absorption spectrum of PMMA and PVDF. (a) Absorbance spectrum of PMMA, PVDF, and their blend measured with attenuated total reflectance Fourier transform infrared
spectroscopy (ATR-FTIR). Both polymers have strong absorption peaks within the atmospheric window. (b). Zero-zenith-angle spectral absorptivity/emissivity of silver-backed PVDF,
PMMA, and their blend films with a thickness of 50 ± 5 mm, measured with UVeVis and infrared spectroscopies in the reflectance mode. (c) Spectral infrared emissivity of silver-
backed PVDF and PMMA films for the zenith angle of 45
. (d) Angular average emissivity of silver-backed PVDF and PMMA films. PVDF, polyvinylidene fluoride; PMMA, poly(methyl
methacrylate).

spectrum of 0.3e2.5 mm and infrared spectrum of 2.5e25 mm. The the solar spectrum, absorption by both polymers is very little owing
PVDF film has an average solar absorptivity of only 3.0%, whereas to the weak solar irradiance and low absorptivity of both polymers
that of the PMMA film is 5.0%, although the PMMA film is visually below the wavelength of 2.5 mm. Therefore, it is difficult to simply
more transparent than the PVDF film. Interestingly, the PVDF- claim that CeF in the PVDF film has lower solar absorptivity than
PMMA blend film has much higher solar absorptivity of nearly CeOeC in the PMMA film. Rather, the macromolecules (PVDF or
10.0%, indicating that it may not be applicable to daytime sub- PMMA) and the silver coating together as a whole are responsible
ambient radiative cooling owing to too strong absorption of solar for the slight solar absorbance of the polymer films. The lower solar
irradiance. The absorptivity/emissivity spectra of both PVDF and absorptivity of the PVDF film may be attributed to its higher crys-
PMMA are weak in the visible and infrared range of the solar tallinity that could scatter and reflect sunlight more strongly.
spectrum and rather high in the short UV range. According to the In the atmospheric window (8e13 mm), the average emissivity of
study by Su [18], UVeVis spectra of polymers generally show only a the PVDF film is 91%, whereas the PMMA film has lower emissivity
small number of peaks. The study further states that UVeVis of 89%. In the infrared region of 2.5 e 7 mm, where emission is not
spectra are most commonly used to detect conjugation because desired, the PMMA film has higher emissivity than the PVDF film. By
molecules without double bonds (C¼C) do not absorb in the UV and comparison, the blend film is less selective than both the PMMA and
visible regions. Because both PVDF and PMMA do not have such PVDF films. The spectral emissivity of the silver-backed PMMA and
double bonds, it can be easily inferred that it is the underlying silver PVDF films for the zenith angle of 45
is given in Fig. 2c, whereas
that absorbs the UV light from the sun. As to the infrared range of their angular average emissivity in the atmospheric window is
4 A. Aili et al. / Materials Today Physics 10 (2019) 100127

given in Fig. 2d. At various zenith angles, the PMMA film has capacity of 1.3 L to store water. Each module has three thermal
noticeably lower emissivity than the PVDF film, with a difference of thermocouples installed from the back side of the PC panel up to its
around 5%. For radiative cooling applications, lower solar absorp- upper inner surface so that the measured temperature is the sur-
tivity and higher infrared emissivity in the atmospheric window are face temperature. One of the thermocouples is located right in the
both important for achieving subambient cooling during daytime. center of the panel, whereas two others are located near the two
Owing to its lower solar absorptivity and higher selective emissivity, opposite upper and lower ends of the panel, respectively. The
the PVDF film is expected to perform much better than the PMMA or module temperature is taken as the simple average reading of the
blend films for daytime radiative cooling. Although lower solar three thermocouples. Thick PET films are coated with a 150-nm
absorption requires smaller film thickness, higher infrared emission silver layer by roll-to-roll physical vapor deposition method.
requires reasonably larger thickness. Note that a very thick polymer These silver-backed PET films are laminated onto the PC panels
film, such as PVDF and PMMA films, most likely becomes a black with adhesive tape that covers the whole panel surface. Here, the
infrared emitter/absorber with noticeably high solar absorptivity. silver side of the film faces the sky and serves as a highly reflective
Depending on the type of polymers, 30e100-mm thickness seems mirror. Double-sided adhesive stripe tapes are then applied along
reasonable, and there exists an optimum thickness or a range of the edges of the PET-silver reflective layer. The PVDF or PMMA
thickness for better daytime radiative cooling performance. We also emissive films are then carefully placed on top of the silver mirror
note that in our previous work [8], the addition of the SiO2 micro- layer and pressed along the stripe tapes. We avoid applying the
sphere results in higher emissivity in the atmospheric window tape over the whole surface because the addition of the adhesive
(8e13-mm wavelength). In this work, we show that polymers with tape results in a noticeable increase in solar absorptivity. The air
certain types of functional groups may also demonstrate higher between the solar-reflective silver layer and infrared-emissive
emissivity than others without the addition of SiO2 microspheres. polymer films is removed as completely as possible by direction-
Water-cooling modules were prepared by laminating freshly ally pressure rolling over the film. We note that we tried to deposit
deposited polyethylene terephthalate (PET)-silver mirrors and the silver directly onto the PMMA and PVDF films by roll-to-roll
emissive PMMA and PVDF films onto twin-wall polycarbonate (PC) physical vapor deposition, but the achieved reflectance is not as
panels, as shown in Fig. 3a and b, following a similar construction high, as shown in Fig. 2b, owing to degradation of the polymer films
procedure and measurement protocol as our earlier work [12]. under high temperature and high energy plasma during the
The blend film was omitted for water cooling tests owing to its deposition. Finally, a thin polyethylene windshield is added to the
high solar absorption. Specifically, two identical modules of modules with a small gap from the emissive surface to minimize
0.6  0.6 cm2 are made of twin-wall PC panels. The modules have a parasitic convection and conduction heat loss.

Fig. 3. Water-cooling modules laminated with silver-backed PVDF and PMMA films. (a) Schematic of the module, highlighting the solar-reflective silver layer and the infrared-
emissive polymer layer. The schematic also illustrates the heat transfer process that involves the solar irradiation, the atmospheric radiation onto the film, the infrared thermal
emission from the film to the sky, and the conduction-convection loss. (b) Photograph of the water-cooling modules laminated with the PVDF and PMMA films. (c) Solar irradiance
in Boulder, CO, during an 8-day measurement period (from 31 August, 2018, eto September 7, 2018). (d) Ambient temperature and the surface temperature of the radiative cooling
modules. The temperature difference between the modules and the ambient can reach as high as 6
C and 4
C during peak sunlight hours and as high as 9
C and 8
C during night
hours for the PVDF and PMMA films, respectively. PC, polycarbonate; PVDF, polyvinylidene fluoride; PMMA, poly(methyl methacrylate); PE, polyethylene.
 A. Aili et al. / Materials Today Physics 10 (2019) 100127 5

Water cooling experiments were carried out over a period of 8 groups' infrared spectrum presents an exciting opportunity to
days during which various weather conditions such as sunny, select from a wide range of polymers for achieving daytime sub-
cloudy, and rainy were observed. As shown in Fig. 3b, the modules ambient radiative cooling. If backed with a highly solar-reflective
are installed with an inclination angle of 15
to pump water more layer, a number of emissive polymers with functional groups of
easily and slightly reduce solar irradiance onto the panels. The solar CeO, CeN, CeCl, and CeF potentially possess the capability of
irradiance is measured with a pyranometer installed in the same daytime subambient radiative cooling. Based on this understand-
aforementioned tilt angle. The ambient temperature is measured ing, we further show subambient radiative cooling of water by
with three thermocouples distributed around the panels. The tip of common polymer films including PVDF and PMMA on a solar-
the thermocouples is sheltered with reflective caps from sunlight reflective layer. The PVDF film cools water below the ambient
while ensuring free air flow. temperature by around 6
C during peak solar hours, and the
The measured solar irradiance and module temperatures are PMMA film cools by around 4
C on summer days during which the
given in Fig. 3c and d, respectively. The sharp drops in solar irra- ambient temperature reaches as high as 20e30
C. Their cooling
diance are due to occasional cloud cover during most days and due performance is even better during nighttime, with PVDF cooling
to rain on September 5, 2018. During most days, either cloudy or water by as much as 9
C and PMMA by as much as 8
C.
sunny, there is noticeable temperature difference between the
modules and the ambient. During the daytime, the subambient
temperature for the PVDF surface can reach as high as 6
C, whereas Conflict of interests
it can only reach 4
C for the PMMA surface. The difference is
mainly due to the lower solar absorptivity of the PVDF film. During The authors declare no competing interests.
nighttime, the subambient temperature drop of the PVDF film is
slightly more than that of the PMMA film, for example, 9
C vs. 8
C,
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