Journal of Nanoparticle Research 4: 157165, 2002. 2002 Kluwer Academic Publishers. Printed in the Netherlands.

Technology and applications

Nanoparticle-doped polymer foils for use in solar control glazing

G.B. Smith1 , C.A. Deller1 , P.D. Swift1 , A. Gentle1 , P.D. Garrett2 and W.K. Fisher2, Department of Applied Physics, University of Technology, Sydney, P.O. Box 123 Broadway, NSW, 2007 Australia (Tel.: +61 2 9514 2224; Fax: +61 2 9514 2219; E-mail: g.smith@uts.edu.au); 2 Solutia Inc., 730 Worcester St, Springeld MA 91151, MA, USA (Tel.: +1 413 730 2572; Fax: +1 413 730 3610; E-mail: PDGARR@solutia.com); Author for correspondence (Tel.: +1 413 730 2107; Fax: +1 413 730 3610; E-mail: wksh@solutia.com)
Received 8 August 2001; accepted in revised form 19 November 2001

Key words: effective medium theory, laminated windows, metal oxides, nanoparticles, NIR absorption, solar control glazing

Abstract Since nanoparticles can provide spectrally selective absorption without scattering they can be used to dope polymers for use in windows, to provide a clear view while strongly attenuating both solar heat gain and UV, at lower cost than alternative technologies. The underlying physics and how it inuences the choice and concentration of nanoparticle materials is outlined. Spectral data, visible and solar transmittance, and solar heat gain coefcient are measured for clear polymers and some laminated glass, in which the polymer layer is doped with conducting oxide nanoparticles. Simple models are shown to apply making general optical design straightforward. Use with clear glass and tinted glass is considered and performance shown to match existing solar control alternatives. A potential for widespread adoption in buildings and cars is clearly demonstrated, and scopes for further improvements are identied, so that ultimately both cost and performance are superior. Introduction The growing commercial availability of nanoparticles has opened up a new low cost option for controlling the light and energy from the sun entering a window. Solar heat and light may enter directly or be reected from the surroundings and it is important in any modication to maintain the central function of most windows, provision of a clear view. The easiest place to incorporate the nanoparticles is in the laminating polymer layer in safety glass, which is essential in cars and trucks, and is used in large commercial buildings in some parts of the world. Cars and trucks have a major solar thermal problem in many geographic zones but existing solutions are expensive and only available in luxury cars. Window lm polymer layers xed to the surface of the glass, or all polymer glazing, could also be used as particle carriers. The potential congurations of the polymers containing the nanoparticles thus fall into
(a) (b) (c)

Glass layer

nanoparticle doped polymer layer

Figure 1. Congurations in which nanoparticle-doped polymer lms can be used in glazing systems.

three basic classes as shown in Figure 1: (i) a polymer layer laminated between sheets of glass with the polymer typically PVB polyvinyl butyral; (ii) a polymer foil, typically PET glued to the glass sheet; and (iii) a clear stand alone polymer glazing panel typically PMMA polymethyl methacrylate or

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Nanoparticles absorb Micrometresized Micrometre particles (or clusters) scatter

(a) Transparent

(b) Translucent

Figure 2. Schematic of haze reduction for transmitted light when incident on (a) nanoparticle-doped polymer as compared to (b) micron-size pigment doped polymer or polymer containing clusters of nanoparticles.

solar radiation. UV blocking is a useful bonus in the materials we discuss. Materials for use in sunscreen pastes and gels for UV blocking such as ZnO, which were traditionally white because of high scattering, are now available in less obvious, clear sunscreens for the same reason, they are now nanoparticles. It was not the whiteness reecting solar radiation that prevented sunburn, but the spectral absorptive properties of ZnO. There has been little published in the general scientic literature on nanoparticles in polymer glazing systems so the underlying science has not as yet received a systematic treatment. However, a number of patents touching on this topic have been published including Kase and Aklyama (1997), Shouji et al. (1996) and Kondo (1998). Parameters of interest in glazing and their measurement Transmittance T () and reectance R() as a function of wavelength and angle of incidence can be measured using a spectrophotometer, while absorptance A() = 1 R T . Calculated properties used for assessment of the solar control capabilities of windows are the visible transmittance (Tvis ) for solar radiation, total solar transmittance (Tsol ), solar absorptance (Asol ), and the solar heat gain coefcient (SHGC), plus CIE color coordinates of transmitted radiation, and haze. The latter is an important check of dispersion quality in the nanoparticle systems. The total solar transmittance is the measured transmittance of a window integrated over the solar wavelength range (3002500 nm) weighted by the solar spectrum. Air Mass 1.5 (AM 1.5), which is equivalent to the spectrum of solar radiation after passing through 1.5 times the perpendicular atmospheric thickness was the standard solar spectrum used for all calculations presented in this paper and is currently the most widely accepted standard. The visible transmittance is the solar transmittance, weighted by the photoptic response of the human eye, which peaks at 555 nm. For normal incidence Xsol = dX()S() , dS() (1)

PC polycarbonate. The rst class is the one widely used in automobiles and trucks, and for safety architectural glass. Why have nanoparticles opened up this option? The key aspect is in Figure 2. Classical inorganic pigment particles such as titanium oxide, barium sulphate or zinc sulphide added to a clear polymer sheet or foil during processing, tend to make it translucent so any transmitted daylight is scattered as shown in Figure 2(b). Thus while they can provide daylight they cannot be used in a window required to provide a clear outside view. They are thus traditionally used when we wish to spread transmitted light to produce even light and reduce glare, as in a polymer skylight or some roof glazings. These pigment particles are typically micron sized. However if the added particles are made smaller and kept apart, transparency can eventually be restored as in Figure 2(a). The sizes required for low haze are typically well under 100 nm, and depend also on the particle refractive index relative to that of the host polymer. The need to keep them separate dictates that concentrations cannot be large and special attention, mechanically and/or chemically, has to be paid to dispersion in production. It is fortunate, as we shall see, that the types of materials needed and the special intrinsic absorbing properties of nanoparticles, allow very low concentrations to achieve the desired control. These separated low concentrations of nonscattering nanoparticles do not cease to have an optical inuence, but can modify transmitted radiation by absorption, and thus if selected carefully according to their absorptive properties, can be used for spectrally selective control of transmitted solar radiation. It can also be used for providing high visible transmittance while blocking the near infra red (NIR) component of

where X() represents T , A or R as measured, and S() is the AM 1.5 solar spectrum. For visible transmittance of daylight we use Tvis = dT ()S()Y () , dS()T () (2)

159
2.0 AM 1.5 Solar Spectrum Spectral Density (W/m2/nm) 1.5 Photopic Response of the Human Eye

1.0

0.5

0.0 300 500 700 900 1100 1300 1500 1700 1900 2100 2300 2500 Wavelength (nm)

Figure 3. Air mass 1.5 spectrum of solar radiation at the earths surface and the photoptic sensitivity spectrum of the human eye.

where Y () is the human eye spectral response, which is shown in Figure 3, along with S(). Xsol , Tsol , R, T and A should also be dened at relevant angles of incidence but it is common to use normal incidence for simple comparisons as data is often not available at non-normal incidence. Note however that other technologies, which we compare to nanoparticle-doped polymers below, have quite different variations with angle of incidence that are important to account for in practice. It is in fact much easier to describe and engineer the nanosystems in this aspect. Often only Tsol and not SHGC is reported, but with an absorbing mechanism from the nanoparticles, there is a signicant rise from Tsol to SHGC with much of the heat entering indirectly. This difference is particularly noticeable when both the glass and the nanoparticle layer absorb strongly. It is worth noting for the purpose of choosing which nanoparticles to use, that around 5055% of the incoming solar energy is at NIR wavelengths and the bulk of this is between 750 and 1100 nm, although S() in Figure 3 extends to 2500 nm. The SHGC is a measure of the fraction of incident solar heat transferred through a window into a room or space. This consists of [Tsol (incident energy)] which is direct, plus the heat re-emitted in a forward direction after absorption by the window, which is indirect. A relationship giving SHGC is thus Asol U . (3) SHGC = Tsol + h0 U is the thermal heat transfer coefcient as dened by ASHRAE, U= 1 L 1 + + h0 hi kt
1

h0 and hi are the thermal conductivities of the outer and inner surfaces of the window, and are dependent on factors such as temperature and wind speed. L is the thickness of the window and kt the thermal conductivity of the window material. Standard summer values as dened in ASHRAE (1997) handbooks are used for all calculations in this work since we are primarily interested in reducing heat gain. Special calculation should be done for cars but for simplicity we use only a vertical window. The CIE Colorimetric System (the CIE 1931 2 Standard Observer) was used for color analysis. Color of radiation is specied by three tristimulus values. Color specications for observers with normal vision are given in terms of chromaticity coordinates, which are a measure of the color quality of transmitted or reected radiation relative to an observer. The relevant equations can be found in Kaye and Laby (1973). Competitive technologies: a comparison to the new nanosystems Granqvist (1991) gives an introduction to advanced glazings for solar control. Before a detailed examination of nanoparticle-doped polymer systems it is worth noting the competitive technologies for solar NIR control in windows both from a technical and a cost perspective. Some of these have been available for a number of years and others are quite recent. Up until a few years ago it has been exclusively done with multilayer thin lms, on the exterior of the glass, or on one surface of a multi-laminate layer between glass (as produced by Viracon), or on a polymer glued to the glass. These multilayers are composed of thin metallic layers dispersed between dielectric layers of high refractive index (such as SnO2 , In2 O3 , TiO2 , ZnO and ZnS). The dielectric layers act as both protectors and anti-reectors for the metal layers, which have low durability if exposed at the surface and are soft, with silver the most commonly used. Spectral selectivity can be tuned by altering the thickness of the layers (Wilson, 1999). They control mainly by reection of the NIR with some absorption, whereas the mechanism we present is absorptive. Other simpler coatings used for reectance include refractory metals such as TiN or stainless steel. These cannot provide high Tvis while blocking the NIR, so lack the spectral control of the nanosystems. A reection mechanism does lead to less heating of the glass and hence less differential between the solar transmittance Tsol and the

(4)

160 SHGC. However, comparable SHGC values to the lms can be achieved with the polymer foils doped with nanoparticles whose main advantage is ease of mass production. A quite new mechanism has been recently demonstrated for metal-free reecting in the NIR which uses only polymer and can be used in laminates (Boettcher, 2001; Shrenk et al., 1991, 1992). It involves a stack of large number of microlayers, in effect a stack of bilayers, where the alternate layers are polymers of different index. Each layer must be precise in thickness, index and uniformity for such a system to achieve its desired reecting properties and should not distort internally on bending. It should be noted that limited NIR absorption is already widely used in most car windscreens in warmer countries, using glass with higher iron content. But there are strong limits to the amount of NIR that can be blocked by tinting in this way because the visibility properties also get affected. Glasses commercially available for many years, such as Solex by PPG, use the absorption of the iron silicates. There has been an advance in the 1990s in this area to yield what are termed, high performance tinting glass, which can achieve the performance of the nanoparticles, but requires an expensive electric arc process to achieve the special oxide additives within the glass. PPG Solextra utilises high-performance tinting. Other competitive possibilities are reported mainly in patents. They include the use of IR absorbing organic dyes in polymer, which are generally quite unstable in bright sunlight, but progress is occurring in dye photostability; another use of nanoparticles is production of thin lms, closely packed layers of nanoparticles directly onto a glass sheet. Sumitomo, ShowCoat and others can supply the coating materials to make such layers. These are easy to apply, but their longterm retention on the surface is an issue, with frequent re-coating possibly required unless other measures are taken. Spectral control with hybrid systems of nanoparticles in polymer along with another absorption mechanism is also quite attractive, the aim being to have the combined absorption spectra giving an optimised performance across the entire solar spectrum for a given application or building situation. The most obvious choice is to combine the nano-tinted polymer with a low-cost tinted glass to keep the cost attractive. The tinted glass should thus absorb radiation where the nanoparticles used have weaker absorption. Nanoparticles for NIR spectrally selective absorption What materials are best as dopant nanoparticles for absorbing the NIR and providing little or moderate visible absorption? The classical pigments noted above have little use as nanoparticle solar absorbers, as they will transmit uniformly well across the solar spectrum. Materials containing moderate densities of mobile electrons are useful for two reasons, they absorb in this range but most importantly they have over all or part of this wavelength range a negative dielectric constant (strictly, the real part of = 1 ). A small spherical particle for example, with a negative value of 1 has an absorption resonance (Bohren & Huffman, 1983; Van der Hulst, 1981) when p1 = 2h (5)

with subscript p denoting particles and h the host polymer matrix. Provided the particle density is low and the particle size is small we can make a quasi-static dipole approximation in which each particles polarizability P is given as in Eq. (6) using basic electrostatics or effective medium theory (Niklasson, 1991) where the real part of the denominator clearly vanishes at the resonance dened by Eq. (5). This creates a maximum in the absorption coefcient, which is proportional to the imaginary part of P (Meeten, 1989). For a sphere of volume V , P is given by P = 3V p h p + 2h (6)

For non-spherical particles, equations similar to (5) and (6) can be found (Skryabin et al., 1997). The absorption strength and bandwidth depends only on the imaginary part of p = p2 , if h is real, though many of the polymers of interest also have weak absorption bands in the NIR. The spectral location of the resonance is the key issue, along with its bandwidth and strength. The enhancement in absorption strength due to the small particle resonance in Eq. (6), makes these nanoparticles much more efcient absorbers per atom or per unit of surface area than the bulk material from which they are made. This efciency is such that we have found in a 0.7 mm thick layer that to achieve the desired response we typically require less than 0.5% by weight of nanoparticles in the polymer. Tuning the resonance location means that we have to nd a material that satises Eq. (5) at a wavelength that is well

161 into the NIR. The resonance peak cannot be in the visible or even just into the NIR if we want no impact on the visible transmittance, because the absorption resonance width may spill excessive absorption over into the visible, if the absorption peak is below around 900 nm. If, however, we wish to also have color tinting and reduced glare, then a lower wavelength peak may be acceptable. Note, however, that such an absorption is likely to be much larger at red wavelengths with ramications for quite distinct colors of transmitted light. Color balancing with other pigments may be needed. Two simple pieces of physics can guide us in selecting materials, namely that as the mobile carrier density decreases the onset of a negative dielectric constant shifts to longer wavelengths and that at wavelengths longer than this onset the dielectric constant gets increasingly negative. Thus as carrier density decreases the resonance shifts to longer wavelengths since the host dielectric constant is approximately xed. The candidates are thus metals or conducting oxides. For metals such as silver and gold it will occur in the visible but the strength of absorption in these particles is such that quite a small quantity of metal nanoparticles may absorb too strongly. Such a window could be almost black or slightly red in appearance. This phenomenon in small metal particles is behind the performance of many solar selective absorbers and their strong absorption across the full solar spectrum (Granqvist, 1989; Smith, 1979). A material with a lower density of free carriers is thus needed for the desired spectral selectivity, with an absorption peak in the NIR and a high Tvis . Oxide conductors are the ideal candidates (though some other materials can be considered). Thus, we will focus on these, in particular indium tin oxide (ITO) and antimony tin oxide (ATO). full performance of a window system of any design, with any number and conguration of glass sheets of specied spectral properties, and any variation in nanoparticle concentration, provided the particles are fully dispersed. That is, having data on one polymer foil sample or window containing a doped polymer of any type with known particle concentration, we can use the results on that system to model any desired variation. The rst step is in effect simply to determine the attenuation coefcient per nanoparticle or equivalently the shift in the imaginary part of the refractive index of the composite (k) per nanoparticle. We have proven this to work accurately in numerous practical cases, one of which appears below. We can if needed, go one step further and do rst principle physics modelling of the spectral transmittance of the nanoparticle-doped polymer. To do this, either of the optical constants of the nanoparticle material must be known. Data in Palik (1999) or Stjerna et al. (1994) can be used if bulk constants sufce, or they can be modelled using simple modied Drude free electron theory. Sometimes an extra inter-band oscillator may be needed as well as the free oscillator (Drude) charge system. In ATO a simple Drude model sufces in the NIR in thin lms (Stjerna et al., 1994), and nanoparticles, with a shift in the constant term in from 1 (due to residual effects of higher frequency oscillators). This works because the onset of absorption is well into the NIR. If particle optical constants are not available or only known approximately, we can, in principle, work back, to determine them from T and R measurements on materials of known particle concentration, and hence nd carrier concentrations. This is easy for the attenuation part as noted above, but at the low concentrations we use, it is difcult to experimentally nd the real part of refractive index for the nanoparticles. Optical constant data also allows a check on such issues as the effect of particle size on electron relaxation time and if any particle shape asymmetries are present. Further details on the modelling and theory will be presented elsewhere with the emphasis here on data and straightforward window models, but we note that while in nano-metal systems electron transport relaxation times fall from the bulk values, in the conducting oxides needed for NIR work the bulk relaxation time is already short enough not to be strongly inuenced by size. Thus, we can use bulk refractive indices for ITO and ATO as a good starting guide, although especially for ATO some variations in the particles occur in carrier concentration, depending

The systems studied We have studied both nanoparticle-doped polymers by themselves where the host is either PMMA sheet or PC thin foil, and laminated glazings, where the host is PVB which is thin and exible by itself, and typically contains a number of other ingredients apart from PVB itself. As well as measuring the spectral, lighting and solar control properties of these systems we have also developed and tested a complete and accurate modelling capability for radiation from any angle. We can determine starting with a given doped polymer the

162 on details of the manufacturing process and relative amounts of tin and antimony oxides. When clustering is not a problem, simple effective medium models, at least for ITO and ATO nanospheres, based on Eq. (6) at optical and NIR wavelengths appear to give a quite accurate optical description of these systems if the particles are well dispersed and scattering is weak or negligible. This is very handy from a design point of view when assessing what concentrations to use for a particular system. Sometimes scattering is evident in the results only at short, blue wavelengths while the simple models work well in the NIR. PC samples were prepared by solvent casting to produce thin layers 0.13 mm for microscopic studies, and optical studies to extract attenuation coefcients for modelling thicker samples. Higher concentrations by factor above 4 were used, compared to sheets used in practice, which will be at least 0.7 mm as a window lm layer or 46 mm if stand alone. In practice PC will be extruded so the nanoparticles will be dispersed within the molding beads. Our PMMA was cast. PVB layers containing nanoparticles were extruded using a Killion extruder. Extrusion temperature was 190 C. The sheet was extruded through a slit die, the take up speed adjusted to give a sheet thickness of 0.076 cm. The laminates were made by hand and subjected to an autoclave cycle of 143 C and 12.7 atm. for an hour. Some excellent low scattering samples were produced in the PVB but care in initial dispersion during formulation of the PVB was still needed. For other polymers, particles were added and well mixed in the relevant solutions at concentrations ranging from 0.2% to 2% by weight. Clustering is more of a problem at the higher concentrations as needed in thin PC. In this PC study simple dispersion techniques in the solvent plus dissolved polymer were used. We show in a PC samples how short wavelength scattering effects can occur but the simple quasi-static models still work in the NIR, while in the good samples the simple models work at all visible and NIR wavelengths. Micrographs from a eld effect SEM were used to study dispersion and check nanoparticle size. Well-dispersed nanoparticles were usually found, especially at concentrations under 0.5% with diameters in the 3040 nm range. Note that the particle volume fractions are needed for use with Eq. (6) which one uses to nd the total dipole moment per unit volume, so if there are N particles per unit volume we need N which is proportional to N V = f , with f the volume fraction. The volume fraction f is calculated from particle mass fractions, and particle and host densities. The density of individual nanoparticles was taken to be 6.8 g cm3 for ATO and 7.1 g cm3 for ITO, and the density of the nal polymer was measured.

Example results A CAREY UV-Vis-NIR spectrophotometer was used to obtain results for specular transmittance and reectance, at select concentrations. Universal modelling parameters were obtained from some of this data for each class of nanoparticle (dened by material and shape) in a given matrix when scattering is absent and tested against a range of other data. The primary parameter of interest is absorption coefcient n () per unit volume fraction of nanoparticles where I = I0 ex denes total attenuation with depth x, so that () = f n ()+(1f )h (), with f the volume fraction of particles and h () the attenuation coefcient of the undoped host polymer at wavelength . This simple linear approach is inaccurate at f values above a few per cent, and its renement will be discussed elsewhere, but it works well at concentrations below 1% which applies to most windows in this study. A universal attenuation factor at each wavelength per volume per cent of nanoparticle material in the polymer can thus be obtained in two ways, from any concentration sample in the same polymer or from a rst principles Drude model of the ATO nanoparticles plus Eq. (6). Either approach allows a study of the full range of possibilities both for high visible transmittance as needed in car windscreens (Tvis > but near 70%) and for applications where a clear view is needed but higher solar control and glare control is also desired (Tvis near 0.38 is one example). Here, we only consider normal incidence and concentrate our results on high Tvis systems, as these are the most demanding in terms of spectral selectivity. The key performance parameters derived from modelled and measured spectral data appear in Table 1 for Tvis windows suitable for cars (Tvis > 70%). The two with an asterisk denotes samples that have been modelled without matching experimental data. The ATO laminate case is based on rst principles models which also work with thin PC plus ATO, as in Figure 4, and the 4 mm thick PC model is based on attenuation coefcients obtained from a thin sample at different concentration. This case is interesting because it shows one can get comparable performance to existing high iron glasses in a clear polymer window with a very low

163
Table 1. High Tvis options. Impact of ITO and ATO nanoparticle doping on laminate systems and clear polymer, and comparison to some existing solar control, high visible transmittance glazings Laminate/glazing system Clear glass laminate Clear glass laminate (ITO 2000 ppm) Clear glass laminate (ATO 2000 ppm) Green glass laminate Green laminate (ITO 2000 ppm) 4 mm PC (ITO 350 ppm) 5 mm Pilkington Evergreen 4 mm PPG Solex laminate 4 mm PPG Solextra laminate Tvis 0.88 0.87 0.83 0.76 0.74 0.70 0.72 0.80 0.70 Tsol 0.73 0.62 0.61 0.51 0.43 0.50 0.42 0.58 0.39 Asol 0.19 0.34 0.32 0.43 0.50 0.44 0.50 0.36 0.56 SHGC 0.78 0.68 0.70
0.2 Transmittance 1.0 0.8 0.6 0.4

0.61 0.56 0.59 0.57 0.69 0.52

0.0 300 500 700 900 1100 1300 1500 1700 1900 2100 2300 2500
Wavelength (nm)

Figure 5. Modelled specular transmittance spectrum for a laminated window with two clear glass panels in which the PVB contains 0.2% by weight of ATO.

1 .0 0 .8 Transmittance 0 .6 0 .4 0 .2 0 .0

Experimental Modelled
Transmittance

1.0 0.8 0.6 0.4 0.2

PPG Clear Laminate PPG Clear | PVB + 0.2% ITO| PPG Clear (Measured) PPG Clear | PVB + 0.2%ITO| PPG Clear (Modeled)

300 500 700 900 1100 1300 1500 1700 1900 2100 2300 2500 Wavelength (nm)

0.0 300 500 700 900 1100 1300 1500 1700 1900 2100 2300 2500 Wavelength (nm)

Figure 4. Measured and modelled specular transmittance spectrum for a thin layer of PC in which nanoparticles are partly clustering. The model assumes specularity and no clustering.

concentration of ITO but the total ITO used per unit area will be equivalent to that in the 0.7 mm thick PVB case. Solar transmittance of polymer apertures such a skylights has been a longstanding problem. Some data from existing competing window technologies for solar control, which have close to the nanoparticle performance also appears in Table 1. Cost and durability are then the discriminating issues. In Figure 4 data appears on a hazy, incompletely dispersed sample of 2% ATO in PC where scattering loss is obvious below 1 m. The degree of haziness depends also on the actual angular spread of scattered light, which here is not large as measured in our photogoniometer, and thus this sample still gave a reasonably clear, only slightly hazy view. It is enough to drop the signal a lot in the specular beam instrument, as shown, and still shows good NIR blocking that can be

Figure 6. Specular transmittance comparison of a laminated window with two clear glass panels and undoped PVB, with one in which the PVB contains 0.2% by weight of ITO. Model curve based on a universal attenuation parameter for ITO spherical nanoparticles in PVB.

accurately modelled. The extension of the model curve shows what should occur if it was fully dispersed at visible wavelengths. Figure 5 shows modelled results using Eq. (6), for 0.2% ATO nanoparticles in 0.7 mm of PVB laminated between two clear PPG glass sheets. The particle refractive indices are the same as used to successfully t NIR PC data. This curve yielded one set of results in Table 1. Figure 6 shows transmittance spectra for a window with two clear PPG sheets around 0.7 mm thick PVB with 0.2% ITO nanoparticles, along with results for the two clear glass laminates with no addition to the PVB. The extra absorption of the nanoparticles in the NIR is obvious in this gure. A model has also been carried out using a separately determined universal attenuation factor for ITO in PVB per cent of ITO,

164
1.0
T (Green glass | PVB | Green glass) T (Green glass| PVB + ITO 0.2%| Green glass)

Transmittance

0.8 0.6 0.4 0.2 0.0 300 500 700 900 1100 1300 1500 1700 1900 2100 2300 2500 Wavelength (nm)

Table 2. Solar control in ITO and ATO nanoparticle-doped PC sheet compared to existing multilayer thin lm laminate systems with similar Tvis Laminate 12.8 mm Viracon solar screen laminate Viracon multilaminate 6 mm PC (5000 ppm ATO) 6 mm PC (1000 ppm ITO) Tvis 0.38 0.38 0.39 0.37 Tsol 0.25 0.15 0.24 0.20 Asol 0.64 0.64 0.71 0.74 SHGC 0.42 0.32 0.38 0.34

Figure 7. Specular transmittance comparison of a laminated window using two low-cost standard car windshield glass panels and undoped PVB, with one in which the PVB contains 0.2% of ITO.

which indicates we can use these factors comfortably to estimate performance at any concentration below a few per cent in any laminate structure and with various glass combinations. Finally in Figure 7 we show the traditional tinted green or high iron glass laminated window as used in cars, such as PPG Solex, without any addition to the PVB. This is compared to what happens with the addition of 0.2% of ITO to the PVB and both solar performances are summarized in Table 1. Both types of model and experimental data agree well in this sample. The combined glass + laminate layer NIR attenuation is quite strong, but this gure shows there is still plenty of opportunity for further cuts in NIR throughput, using either different nanoparticles in addition, or various combined approaches to absorption in the range 7501100 nm, where NIR solar energy (see Figure 3) is strongest. To do this and not affect Tvis and transmitted color is not easy. Hence much lower solar input should be obtainable for architectural windows with moderate Tvis using nanoparticles combined with other absorption mechanisms in the glasses or the PVB. Combinations of nanoparticles, and colorbalancing pigments as necessary, may provide one lowcost solution to additional solar control and will be subject to future analysis. To see how far we can go with the two-nanoparticle types by themselves, as used in this study, we show models for thicker panels of PC polymer in Table 2 and compare two commercial multilayer alternatives. Concentrations of nanoparticle at these thicknesses are still low but if we want to add them to PVB in a laminate concentrations would be undesirably high and the best option then is to combine

with spectrally complementary nanoparticles, or other absorbing mechanisms, including tinted glass. The fact ITO clearly gives better solar blocking performance than ATO is seen in all of the data presented, especially in Table 2 where it outperforms ATO despite having one-fth its concentration. This is due to its onset of absorptance being at shorter wavelengths than ATO (compare Figures 57). Unfortunately, ITO costs much more than ATO with indium being scarce, but the lower concentrations reduce the cost differential. For the glare blocking architectural windows it can be seen in Table 2 that SHGC with the nanoparticle solution, should be able to match or improve on existing approaches and in a hybrid absorber should be much lower in cost. We note that both types of nanoparticle-doped sheets at these concentrations almost completely block the UVB component of incoming solar energy since the particles interband absorption is strong in the UV. This is a useful addition to the protective value of these windows. Chromaticity coordinates for transmitted daylight when the particles are fully disperse, are closer to neutral in ATO than ITO because it has a longer wavelength onset of absorption, but ITO doped sheet also gives a reasonable neutral colored light. For example the CIE color coordinates are x = 0.312, y = 0.343 with the clear glass ITO laminate in Figure 6. Conclusions Nanoparticle doped polymers can provide laminated windows and polymer glazings for good solar control with high visual and daylighting performance. The ability of nanoparticles made of certain conducting material to resonantly absorb, especially in the NIR, is the key to the appeal of this technology. They can match the performance of the available multilayer coatings on glass and especially on high-performance glasses. ATO nanoparticles are less able to block solar heat than ITO particles, but may have applications with other

165 complementary absorbing processes, having the benet of much lower cost. There is considerable scope for further improvements even when Tvis > 70%, where an SHGC approaching 0.4 may be achievable with the aid of nanoparticles. The potential benets to passengers in cars and occupants in buildings, and hence to energy savings and safety of this technology in warm climates is very high. References
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