Inorganic or organic substances that are insoluble or substantially insoluble in water or organic medium.

Impart colour, opacity ,mechanical rigidity and reinforcement to the continuous phase in which they are dispersed.[1] Impart certain special properties to the coatings such as reflection of infrared radiation.[2] Pigments can differ in their weatherability, chemical resistance, and other durability criteria. Pigments are classified on the basis of their performance as decorative and protective . Alter the appearance of the coating by selective absorption or by scattering of light.

The suns energy that reaches the earths surface is divided in to three main parts.(Fig 1) UV - 5% Visible - 43% Infra red - 52% The heat-producing region of the infrared radiations ranges from 700 1100 nm. These radiations on absorption result in heating up of the surface[1] Coatings colored with conventional inorganic pigments tend to absorb the invisible near-infrared (NIR) radiation.

Spectral Solar PowerDistribution

Researchers are developing new complex inorganic pigments that exhibit dark color in the visible spectrum and high reflectance in the near infrared. This class of pigments increases the near infrared reflectance of exterior finishes and paints, there by dropping the surface temperatures of roofs and walls. The inorganic NIR reflective pigments are mainly metal oxides and are primarily useful in two major applications: (i) visual camouflage and (ii) reducing heat build up.

Infrared reflective inorganic pigments are complex inorganic color pigments, which reflect the wavelengths in infrared region in addition to reflecting some visible light selectively. The reflectivity and absorptivity of the pigment are independent of each other. Thus an IR reflective pigment may have any color. They do not absorb in near infrared region. They either reflect it or transmit it. Their refractive index is different from that of the binder in the infrared region. This causes diffused reflection in IR region. If the refractive index of the pigments in the IR region is similar to that of the binders refractive index in the IR region, the pigment would be transparent to near infrared light . In such a case, any reflection in the near infrared region would be due to undercoat.

Absorption of light occurs when light energy promotes electrons from one bonding state to another. If light of a different wavelength is used to cause this energy transition, it will not be absorbed e.g. iron chrome blacks absorb light through the visible region. This means there are electronic transitions responsible for absorbing light with wavelengths of energy from 400 - 700 nm. Light of lower energy (>700nm) is not absorbed. In this case, a beam of light with a wavelength of 1500 nm is too low in energy to cause any electronic transitions in the material. Thus it will not be absorbed. Instead the 1500 nm light beam is refracted,r eflected and scattered leading to diffuse reflection of NIR light.

Pigments are synthesized by subjecting mixtures of metal hydroxides, nitrates, acetates or even oxides, to very high temperatures by calcination. Metal oxides or salts are blended together and strongly heated, generally at temperatures of over 1000C. At the calcining temperature the solids themselves become reactive. Metal and oxygen ions in the solids rearrange to form new, more stable crystal structures [4].

Individual Pigment selection: Pigments having highest reflectivity in the near infrared region must be selected for making infrared reflective coatings. Dispersion: These pigments are compatible with all types of solvent and water-based coating systems such as acrylics, polyesters and fluoropolymer systems.

Representation of CIE lab system

Blending pigments: A combination of two infrared reflective pigments can increase the total reflection of the coating. But in some cases where different pigments absorb in different regions, the total reflectance becomes less than the reflectance of the individual pigments. Opacity :The infrared reflective pigments have high visible opacity. These pigments only scatter or transmit the infrared radiations. higher coating thickness may be required for the coating to be opaque to infrared. Pigment volume concentration also plays an important role in deciding the opacity of a coating to infrared radiations.

Contamination :Contamination occurs when two infrared reflecting pigments absorbing at different regions are mixed together. It drastically affect the total solar reflectance on the coatings [3] Particle Size: For highest reflectivity, the particle size should be more than half the wave length of the light to be reflected. Thus for reflecting infra red light of 700-1100 nanometers wave length, particle size should be at least 0.35 to 0.55 microns [2]. Excessive grinding and dispersion may therefore be counter productive.

General benefits Longer life-cycle due to less polymer degradation and thermal expansion due to lower temperature. Aesthetically pleasing colors. Cooler to touch for better handling. Improved system durability and less thermal degradation. Roofing benefits Less heat to transfer into buildings. Reduced Urban heat island effect. Low energy demand for air conditioning, particularly in equatorial regions.

Reduction in air pollution due to low energy usage, power plant emissions, and reduction in urban air temperatures. Installation crews can work longer during the day before the roof gets too hot to work on. Very high durability coatings. Some coatings have been in use for as long as 25 years[1]

The amount of total energy absorbed and emitted by a topcoat determines the heat build-up of a coated surface and results in a final surface temperature after reaching an equilibrium state. Coating pigmentation has the main influence on heat build-up performance. Pigment reflects infrared radiation (heat) from the sun and keeps the coated item cooler, independent of the color of the coating. This can help to minimize air conditioning unit work load and operational cost. Increasing the cooling load of the air conditioning unit may lead to the release of Chloro fluoro carbons(CFC) Automobile engines are being downsized to reduce the weight and improve fuel economy.

They are less able to handle the power drain of the larger air conditioners . Thus, there is a need for new technologies to reduce the solar heat loads and to allow reduction of air conditioner size. IR reflecting pigments would result in reduced CFC emission and increased vehicle fuel efficiency. Over all reduction of carbondioxide emanating from fossil fuels can be possible by this way.

Smarts New Electric Vehicle:Heat shield made of reflective pigments

The reflector ,the dog coat that takes the heat out of the heat To achieve cool surfaces, the pigments need to reflect as much energy as possible. This reflection ability can be expressed as the Total Solar Reflectance value (100%=total reflection; 0 % = total absorption). Pigments with high TSR values show a high reflection combined with low heat build-up, and vice versa. TiO2 , a white pigment with a high NIR solar reflectance of about 87.0% [22] is currently regarded as the best pigment for coating materials. One prefers a dark colour instead of white, while pigments with the lowest reflection are based on carbon black.

There is a choice of using dark inorganic complex pigments like Chromium Iron Oxide with a medium IR reflectivity (50-57%) [22]and showing higher TSR vaues than carbon black. A maximum NIR reflectance of 82.8% is reported for pigments prepared from a composition of Cr2O3, TiO2, Al2O3 and V2O5 of 80, 4, 14, and 2wt% respectively.[23] 6g of this pigment powder in 10g ceramic glaze gives a NIR reflectance of 74.5% and is useful for reflective ceramic roof coating. The near-IR reflective property of the Ga doped ZnO film (72%) is much better than that of the most reported IR-reflective ZnO:Al films(<60%) at 2500 nm and is useful as heat reflector or window coating.[21]

To camouflage military equipment and personnel, synthetic green pigments are incorporated into the coatings. Conventional green pigments do not resemble chlorophyll in the infrared region. They absorb infrared light, whereas chlorophyll reflects it.[10] However, when sophisticated infrared imaging technology is used, it is still possible to see the signature of personnel or equipment against the reflective profile of the background. Each object has its own reflective profile that differentiates it from the surrounding when observed through infrared viewing devices. The infra red reflective coatings have the ability to reflect electromagnetic waves in such a way that they give the same

signature to the observed object as the signature of the surrounding environment, both in the visible (VIS) and near infrared (NIR) spectra. Near infrared is not visible to the human eye, but can be detected by special infrared viewing devices. The reflection of infrared radiation by a coating is controlled primarily by the reflective profile and particle size of the pigments in the coating. All pigments used have been evaluated for reflectance, transparency and hiding power in the near infrared region. They can disrupt the contours of objects, leading to a blurred image for the observer. Even when using specialised viewing devices the object will blend in with the natural environment.

Non camouflage clothing

Camouflage Clothing

This reduces the susceptibility to infrared surveillance devices and can improve the survivability of military assets, leading to improved effectiveness and reduced casualties. Chromium oxide (Cr2O3) green pigments have already been used in camouflage coating by armies for preventing from detection of objects purpose with 50-57% NIR solar reflectance range.[22] US Patent US6468647 describes the use of colored metallic pigments such as aluminum and mica flakes for good infrared reflectivity.[11] According to the patent, color has been incorporated on the metallic surfaces in such a way that it does not interfere with the ability of metallic pigments to control infrared reflectivity.

Most of the literature on NIR reflective pigments exists as patents which indicate their vast potential application. NIR reflective pigments have been used in the military, construction, plastics and ink industries.They can also be useful for camouflage applications. Solid solutions having corundum-hematite crystal structure were found to possess high NIR reflectance and these materials serve as coloring pigments in camouflage paints.[12] The other reported inorganic pigments include (i) composites consisting of a coloring agent and a white pigment (e.g., TiO2) coated with another non-NIR absorbing pigment,[13], (ii) metal coated particles and pigments

(iii) polyolefin compositions containing a blackcolored pigment such as chromium-iron oxide[15] iv) bismuth manganese oxide pigments that can be used as additives in plastics and paints[16] (v) Cr2O3-Fe2O3 mixtures along with additives in a polymer with an IR reflectance of about 68%,[17] (vi) pigments such as titanium dioxide, iron oxide, and chromium oxide with an effective size range from 1 to 8 m[18] (vii) zirconium dioxide modified by silicon dioxide,[19]and (viii)manganese vanadium oxide pigments such as Mn2V2O7, alkaline earth manganese oxides and bismuth manganese oxides[20]

Complex inorganic pigments based on mixed metal oxides (eg., chromium green, cobalt blue, cadmium stannate, lead chromate, cadmium yellow and chrome titanate yellow), which have been used in camouflage, absorb visible light but reflect the NIR portion of incident radiation .[22] Unfortunately, many of the inorganic pigments which are suitable for these applications generally comprise toxic metal ions like cadmium, lead, chromium and cobalt. The use of these metal ions is becoming increasingly strictly controlled, because of their very high toxicity. There is a need to develop novel colored, NIR reflecting inorganic pigments that are less hazardous to the environment.

Industrial utilization of rare earths is growing very rapidly because of their known low toxicity [5] Rare earth elements offer a vast opportunity for development of environmentally secure alternatives for many of the ecoconstrained colorants.

Green Pigments Recently, a new inorganic pigment based on rare earth phosphate (CaCePO4) has been reported[26] The origin of the colour has been attributed to the substitution of the trivalent cerium ions by divalent calcium ions creating oxide ion vacancy in the CePO4lattice and this defect formation is responsible for change in band gap. U V Varadaraju et .al reported a series of Ca-doped PrPO4 compounds with the general formula, Pr1-xCaxPO4 (x = 00.4 in steps of 0.1) that has excellent brightness as well as green and yellow components compared to Ca doped CePO4 and toxic chromium oxide[6]

Orange and yellow pigments P. Sulcova and E. Prokleskova et.al reported new pigments having the formula (Bi2O3) 0.7(Ln2O3) 0.3 with various rare earth cations (Ln = Eu, Gd,Tm, Yb and Lu) Incorporation of doped Ln3+ ions into the host lattice of Bi2O3 colours provide interesting colour hues from yellow to orange[25] Investigated pigments have the maximum reflectance at wavelength 700 nm.(74-86%) Compounds containing Yb, Lu and Tm provide intensive orange colour hue.(H =66-69 )[7] Colour Hue Pigments with Eu and Gd possess orange Red 0-35 yellow (H =76) and intensive yellow colour Orange 35-70 (H =85) respectively. Yellow 70-105

These pigments are resistant to heat and represent potential alternative of inorganic pigments containing chromium and lead (chromate yellows). It is reported zirconia rare earth mixed oxides ZrCe1-xYxO4- and ZrCe1-xPrxO4- by solution combustion method with a reflectance of 90% at wavelength above 550 nm.[8] It exhibits yellow color when doped with Y and changes from yellow to orange-red color when doped with Pr, with increase in x values. Mica coated with rare earth oxides (CeO2, PrO2 and Ce0.95Pr0.05O2) showed yellow ,black and orange colour respectively.[9] Mica is obtained from Muscovite, a Brazilian natural source and the pigments were prepared by hydrolysis.[9]

Red Pigments A pigment with Erbium (Er6MoO12)is reported with orangeyellow colours. The compound AxB(2-x-y)CryO3 (A = rare earth and B= Al) produced a variety of shades of red and yellow colour depending on the rare earth, the value of x and y, and the calcination temperature. An intense brownish-red colour was obtained when the rare earth Erbium was used with x=1, y = 0.06 But these two pigments with Erbium are found to be unstable in commercial glaze.[27] Pigments based on rare earth manganese oxides, (RExMn)Oy (RE ) =Y, Ca, Ce, Pr, Nd, and Sm) are reported with an IR reflectivity >50%[14]

Y6MoO12 exhibits 92% NIR reflectance at 1100 nm region. Doping of Praseodymium gives brick red colour with 88% NIR reflectance. Doping of Silicon gives yellow pigments with NIR reflectance 98%. The pigments Y2Ce1.5Mo0.5O7 exhibited yellow and reddish brown respectively with high NIR reflectivity(>90%) and Y2Ce1.7Pr0.3O7 showed colours from brick red to dark brown with good reflectivity.[24] Blue Pigments Intense blue colour is reported with YIn0.9Mn0.1O3 and the colour darkens with increasing Mn concentration.

Pigment Y2BaCuO5, Sm2BaCuO5 and Yb2BaCuO5

(Bi2O3) 0.7(Ln2O3) 0.3 (Ln=Eu,Gd,Tm,Yb,Lu)

Colour Green

Remarks Thermally/chemically stable

Yellow-orange

Reflectance(74-86%) Heat resistant

Sm2Ce2-xMoxO7+ (x = 0 to 0.4) Ce1-xMxW2O8 (M = Zr or Ti, 0 < x < 0.6) Ca-doped Nd2S3 ZrCe1-xYxO4- ZrCe1-xPrxO4- TiCe1-xPrxO4- Sm2Ce2-xPrxO7+ (x = 0 to 0.4) CePS4, Ce6Si4S17, and Ce4Si3S12

Cream to yellow Intense yellow Green Yellow Orange red Brick red Dark brown Yellow chromatic properties similar to CdS, PbCrO4 and PbMoO4,thermally/chemically stable Reflectnce-90%

Industry has realized the potential of pigments for various applications and the research is focused on developing hygienically and environmentally friendly rare earth based pigments. There is no known method to predict the infrared reflectivity of any substance. The only technique to find out if a pigment reflects infrared radiations is to test its reflectivity. Any specific physical property of the pigment cannot be correlated with its infrared reflectivity. It should be possible to screen a large number of inorganic pigments manufactured so far to look for IR reflecting pigments.