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(54) COMPOSITION OFATHERMALY (52) US. Cl. ....................... .. 106/409; 106/486; 106/417;
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COMPOSITION OF A THERMALY INSULATING [0009] The results With respect to masstone shoW insig
COATING SYSTEM ni?cant differences betWeen the tWo pigments. In tint, hoW
ever, is found that the pigment of Example 1 has a 3%
STATEMENTS AND REFERENCES strength advantage over the pigment of Example A, and this
is believed to be due to the ?ner particle siZe.
[0001] Reference: Provisional application No.60/525,683
?ling date Dec. 1, 2003, Composition of a thermally insu [0010] Nothing further is described for coating systems.
lating coating system, Anthony D. Skelhorn. The patent does describe use in PVC sidings as folloWs: one
desirable characteristic of the pigments and other additives
BACKGROUND OF INVENTION that are blended With the vinyl chloride is their ability to
re?ect infra red rays. A highly infra red re?ective siding Will
[0002] Compositions that may be used to thermally insu remain cooler When exposed to sunlight than a siding
late other materials, especially from the effect of intense containing additives Which readily absorb many of these
sunlight, have a number of potential applications: Examples
infra red rays. Lower temperatures mean a loWer heat
include among others:
build-up Within the structure and longer life for the siding.
[0003] a) Insulation of structures (eg a house or A reduction of a feW degrees in the heat build-up translates
hotel) to reduce energy consumption, especially dur into a substantial increase in the life of the siding. No further
ing summer months in southern regions. quanti?cation of the infra red re?ectivity effect is described
or hoW to formulate to maximiZe the effect.
[0004] b) Insulation of ?ooring material (such as
Wood or concrete) to reduce the temperature, thus [0011] US. Pat. No. 5,607,995 describes a paint compo
alloWing, for example, bare-foot passage on a patio sition Which comprises a binder to impart ?lm forming
or deck. properties compounded With quasi transparent polyole?n
[0005] c) Insulation of heat sensitive equipment such ?ller particles having a particle siZe beloW 110 micrometers,
as is used in military and civilian applications, alloW said polyole?n being selected from the group consisting of
ing improved operational ef?ciency by reducing the a polyethylene, a polypropylene, copolymers of ethylene
in?uence of heat on internal components under ardu and propylene and mixtures thereof, said polyole?n ?ller
ous conditions, such as desert environment. particles being present in an amount betWeen 0.1% to 10%
by Weight of the composition. These paint compositions
[0006] The invention describes a method of preparing a Were found to possess loW gloss and matte properties at
paint system (paint or paint plus primer) Which offers a visible and high re?ectance in the thermal infra-red Wave
solution to the problem of solar heating. Moreover the lengths.
material may be applied by conventional methods, such as
brush, spray or roller, and may be applied during original [0012] US. Pat. No. 5,650,461 describes a paint compo
part preparation or retroactively after a product has been sitions Which provide a Chemical Agent Resistant Coating
manufactured or placed in service. (CARC), consisting of one layer topcoat paint system, Which
imparts an increase in the re?ectivity at the thermal infra-red
[0007] Infra red re?ecting compositions have been pro
duced using a number of approaches. US. Pat. No. 5,006, region, While controlling the colour in the visible range and
175 describes a broWn rutile pigment composition from are maintaining a loW gloss, comprising: an extender
about 40 to about 50% by Weight of titanium, from about 2.3 selected from polyole?ns and substituted polyole?ns; a
to about 4.5% by Weight of manganese, from about 7.3 to pigment, selected from a metal oxide calcined at a tempera
about 11 % by Weight of tungsten, from 0.05 to about 5% of ture of above 600.degree. C. and a paste of metal ?akes and
lithium and from about 0.1 to about 20% of cerium. Use of any mixture thereof; a binder consisting of a modi?ed
the broWn rutile pigment is described in rigid vinyl and polyurethane resulted from an isocyanate and a co-reactant
alkyd paint and is described as infra red re?ective betWeen possessing at least tWo hydroxy groups, and a solvent system
700-1000 nm. to dissolve the components in the paint composition.
[0008] The patent describes Color values in masstone and [0013] US. Pat. No. 5,713,974 describes Evacuated
tint Were tested using a conventional laboratory paint shaker micro-spheres, insulating materials constructed from such
method, dispersing the pigments in an air-dry enamel micro-spheres, and methods of manufacturing same provide
vehicle, and grinding for 20 minutes on a paint shaker in a insulation and reduce heat transfer through radiation, con
glass jar With glass beads. The tint Was calculated as 50% duction and convection. Additionally, an infrared re?ective
pigment and 50% titanium dioxide. The dispersion Was then coating is provided on a microsphere surface to reduce
draWn doWn on a Leneta opacity chart. Color differences
Were evaluated using the Diano Match-Scan Spectropho radiant heat transfer. A protective exterior coating is also
tometer and expressed in Hunter values. Tint strength dif provided to protect an exteriorly applied infrared re?ective
ferences Were calculated using the K/S ?gure at 460 nanom coating on such a microsphere. Furthermore, the spheroidal
eters. The differences betWeen the pigment of Example 1 geometry of such micro-spheres restricts heat transfer to
and the pigment of Example AWere found to be as folloWs: point-to-point conduction there betWeen. Finally, evacuated
micro-spheres further reduce through-heat transfer Within a
TABLE II shell. One embodiment utiliZes such evacuated micro
spheres in constructing an elastomeric roof coating Which
DE LD RG YB appreciably reduces cooling and air conditioning poWer
Masstone: 0.18 —0.13 —0.09 —0.09
costs for a building. An alternative embodiment utiliZes such
Tint (1:1) 0.27 —0.26 0.01 —0.07 an elastomeric coating in constructing an exterior paint for
a building. A method of evacuating such micro-spheres
involves in-permeation of selected gases Within a micro
US 2005/0126441 A1 Jun. 16, 2005
sphere that reacts under sufficiently high temperatures With absorption of electromagnetic radiation in the infra red
residual gases Within the microsphere to produce by-product region of the spectrum, commonly described as heat, plus
gases Which out-permeate from Within the sphere under use of materials Which reduce conductive heat transfer. The
sufficiently high temperatures. Furthermore, a method of system is designed to act as an insulating material in
constructing suitable glass microspheres Which are suitable applications Where infra red radiation levels are signi?cant,
for evacuating via out-permeation is also described. such as bright sunlight.
[0014] The patent focuses on the method of production of [0018] This Thermal Coating can be pigmented to produce
the evacuated micro-spheres and describes their use in an conventional colors, and is especially valuable for darker
exterior coating formulation as folloWs: “The evacuated colored coatings, and Which may be smooth or textured, ?at
shells 12 provide a crucial component in formulating a or glossy, according to normal de?nitions used Within the
coating 32 Which alloWs attainment of appreciably coatings industry.
decreased thermal conductivity, and helps develop and
retain a high re?ectivity to solar and other infra-red radia [0019] A Thermal Primer is essential for some applica
tion. A combination of long-term high IR re?ectivity and tions Where it is required to provide good adhesion betWeen
loW thermal conductivity decreases the energy loading, the substrate under consideration and the Thermal Coating
resulting from absorption and transference of heat, into a top coat. If a primer is required, then it is desirable to
coated enclosure. For example, such a coating 32 could be incorporate thermally insulating materials, such as are speci
utiliZed Within an infra-red oven to retain heat more effi ?ed in the “Thermal Coating” in order to further reduce
ciently therein and enhancing the cooking operation of conductive heat transfer.
process.” [0020] The Coating System has been designed in such a
[0015] The patent itself teaches nothing about speci?c Way that it may be used in combination With a broad range
Wavelength effects, nor does it teach hoW to maximiZe IR of binder materials, for instance Water based polymers such
re?ectance of a coating or other composite material by as acrylic homopolymers or copolymers or other conven
formulating With other materials to gain an increased effect. tional latex based or Water soluble binders, or solvent based
systems such as alkyd polymers, silicone, urethane 1-part or
[0016] US. Pat. Nos. 6,174,360 B1 and 6,454,848 B2 2-part systems or other solvent based binder, even in Ther
describe neW solid solutions having a corundum-hematite moset polymers and copolymers, such as unsaturated poly
crystalline structure Which are useful as inorganic pigments. esters or epoxy systems. The coatings may be produced by
Solid solutions according tot he present invention include a brush, spray or electrostatic technique, or by molding, or
host component having a corundum-hematite crystalline may be applied to thermoplastic systems such as PVC,
structure Which contains as guest components one or more Polypropylene, Polyethylene, thermoplastic epoxy com
elements from the group consisting of aluminum, antimony, pound, thermoplastic polyester or other thermoplastic poly
bismuth, boron, chrome, cobalt, gallium, indium, iron, lan mers Which may be used to fabricate systems such as poWder
thanum, lithium, magnesium, manganese, molybdenum, coatings, extruded pro?les, or molded products using ther
neodymium, nickel, niobium, silicon, tin, titanium, vana moplastic processing techniques, or may use a cold setting
dium, and Zinc. Solid solutions according to the present technique, or may be cement or gypsum-based.
invention are formed by thoroughly mixing compounds,
usually metal oxides or precursors thereof, Which contain BRIEF DESCRIPTION OF DRAWINGS
the host and guest components and then calcining the
compounds to form the solid solutions having corundum [0021] FIG. 1 shoWs the Solar Spectrum at sea level given
hematite crystalline structure. Some of the neW solid solu in ASTM E490
tions according to the present invention exhibit relatively [0022] FIG. 2 shoWs an alternative method of represent
loW Y CIE tri-stimulus values and relatively high near ing the ASTM E490 solar spectrum in terms of the % energy
infrared re?ectance. The patent suggests these solid solution by Wavelength band.
pigments may be suitable as pigments in the general paint
and polymer markets Where increased near infrared re?ec [0023] FIG. 3 shoWs a typical calibration chart for the
tance Would result in loW heat build-up and thus loWer TC-1000 Thermal Comparator using four relevant standard
energy costs. materials: Expanded Polystyrene, Polypropylene, PTFE and
Calcite.
SUMMARY OF INVENTION
[0024] FIG. 4 shoWs Thermal Conductivity measurements
[0017] The purpose of the present invention is to provide of 30% PVC paint ?lms of different thickness’ using a
a composition description that alloWs a “Coating System” TC-1000 Thermal Comparator With a modi?ed sample
comprised of either one or tWo layers, being a “Thermal immobiliZation ring (inset).
Coating” and, optionally, a “Thermal Primer”. The Coating [0025] FIG. 5 shoWs the re?ectance spectra for three
System is designed With high infra red re?ectivity plus coatings; tWo green Thermal coatings based on re?ective
reduced thermal conductivity, and may be formulated to any pigments and re?ective pigment plus re?ective extender
desirable color. This approach is especially bene?cial if pigment.
darker colored coatings are desired, since these are often
considered to be most heat absorbing. The Coating System [0026] FIG. 6 shoWs the construction of three, tWo foot
is designed to reduce heat transfer from the environment to cubes Which Were constructed to measure both surface and
the substrate that is protected by the Coating System by internal temperatures after coating their exterior With three
formulating to reduce both radiant and conductive heating. different coatings of the same color speci?cation, de?ned by
The Coating System provides a mechanism for reducing their CIE L*, a*, b* values.
US 2005/0126441 A1 Jun. 16, 2005
[0027] FIG. 7 shows the internal temperatures of the The use of the materials described alloWs for a Wide range
cubes depicted in Drawing 1, measured over a 12-hour of materials to be prepared, Which in turn alloWs the system
period in Arizona. to be formulated for a broad range of applications. Typical
applications include, but are not exclusive to: Coatings for
[0028] FIG. 8 shoWs the External temperatures of the
cubes depicted in Drawing 1, measured over a 12-hour the exterior of constructions (houses, o?ices, hotels, etc.),
period in AriZona. Coating for concrete, Wood, plastics or other materials used
for Walkways, such as patios, pools, decks, etc., Coating of
[0029] FIG. 9 shoWs the re?ectance spectra for the cubes vehicles used for transportation, coating of products for
depicted in Drawing 1 for Conventional and Thermal Coat military applications Which are sensitive to heat effects due
ing With equivalent CIE L*, a* and b* color space values. to, eg infra red radiation, coatings for optical systems such
as cameras, scopes or thermal imaging systems, and many
[0030] FIG. 10 ShoWs thermal conductivities of Conven other uses.
tional Coating and Thermal Coating applied to the test cubes
depicted in DraWing 1. [0036] The coating materials may be formulated using the
described materials under a Wide range of loadings. Most
[0031] FIG. 11 shoWs the measured temperatures of applications Will require use at a level beloW Critical Pig
equipment coated With black colored conventional infrared ment Volume Concentration (cPVC), especially if the use is
re?ective CARC and Thermal Coating based CARC versus to be for outdoors or for protective use. On the other hand,
ambient temperature. materials may also be formulated at levels knoWn to be near
[0032] FIG. 12 shoWed the re?ectance spectra for black or above cPVC if the application alloWs for high loadings to
conventional pigmented CARC and Thermal Coating based be accommodated by the formulation.
CARC. [0037] The Coating System comprises either one or tWo
[0033] FIG. 13 shoWs the thermal conductivities of three layers of coating material applied to a substrate, or may be
different CARC formulations based on conventional pig de?ned also as the exterior surface of a material if the infra
ment, infrared re?ective pigment and Thermal Coating red re?ective components are incorporated into a product
based CARC. Which is fabricated other than by application of a coating.
[0038] The Thermal Coating layer contains tWo or more
DETAILED DESCRIPTION OF THE materials from the folloWing groups of materials:
INVENTION
[0039] 1) Extender pigments having a high re?ectiv
[0034] The present invention is directed to the preparation ity in the infra red region of the electromagnetic
of a Coating System, using a combination of materials spectrum relative to the visible region (i.e. has an
described beloW used as a pigment and/or extender pigment Infra Red Re?ectivity Index greater than 1.0 see
(?ller) system to produce an infrared re?ective effect in example beloW),
conjunction With a loW thermal conductivity in a ?lled
composite. This is designed for, but not limited to, a Coating
[0040] 2) HolloW micro-spheres made of glass,
ceramic material or organic polymer
System, Which may be applied to a variety of material
substrates, used either alone as a Thermal Coating, or in [0041] 3) Infra-red re?ective primary pigmenting
combination With a Thermal Primer, as required. Formula materials.
tion principles are conventional, except for the focus on the
use of materials Which have been found to have a high infra [0042] The Thermal Primer, Where required, should be
red re?ectivity and/or loW thermal conductivity. These mate designed to meet the requirements for good adhesion
betWeen the substrate and the Thermal Coating using con
rials, When used in combination of at least any tWo material
classes and preferably a combination of all three material ventional formulating techniques. It has been found to be
advantageous to include a holloW micro-sphere based on
classes Will result in a Thermal Coating, characteriZed by a
high infra red re?ectivity PLUS a loW thermal conductivity glass, ceramic or polymer; and/or extender pigment With
loW thermal conductivity characteristics Which have been
signature. In some instances, it may be necessary to utiliZe
found to enhance the thermal properties of the coating
a primer layer, a Thermal Primer, as a part of the system in
order to provide the level of adhesion needed to insure System.
compatibility betWeen the substrate and the Thermal Coat [0043] 1) Extender pigments commonly used in the coat
ing. It has been found that, in the event that a primer coating ings and other industries all have different re?ectance char
is required, that the incorporation of holloW micro-sphere acteristics described by their solar re?ectance spectra. This
?ller and/or other loW conductivity extender pigments into is particularly important to consider the infra red region of
the primer system is an effective alternative or complement the solar spectrum if materials are to be used to re?ect in
to use in the Thermal Coating to reduce the thermal con these Wavelengths. These materials are usually considered
ductivity of the system. for use based on their visible re?ectance behavior and are
selected because of their contribution to visible color, White,
[0035] The composite material, in the form of a Coating
red, green, blue etc. HoWever, their contribution to infrared
System (paint), may be based on any polymer-based mate
re?ectance is often not considered. It has been found that
rial, may be Water based or solvent-based, single component several materials have infra red re?ectance spectra Which
or multi-component paint or polymer system, or on cement
or gypsum based system. This is because the thermal char
shoW advantageous properties When composition design is
for re?ectivity in the infra red region.
acteristics have been found to be a function of the re?ectivity
and/or thermal conductivity of the components and not the [0044] Examples of extender pigments are calcium car
polymeric, cement-based or gypsum-based binder systems. bonate (both naturally ground and precipitated), crystalline
US 2005/0126441 A1 Jun. 16, 2005
With a 2 inch high speed disperser blade at 7500 rpm for 5 [0059] Thermal conductivity measurements Were made
minutes. The paint samples Were used to prepare a paint using a T-C 1000 Thermal Comparator (Lafayette Instru
draW-doWn on Leneta draWdoWn card, type 5DX, using an ment Company). The method uses an insulated mass that has
8-path precision Wet ?lm applicator at 3 mils (75 microns) ?ne temperature control using a controlled electrical heating
application thickness. The coatings Were alloWed to dry for element. For this study the mass Was heated to 10010.1
1 Week after Which re?ectance values Were determined for degrees Celsius While ambient temperature Was 25 degrees
Wavelengths from 250 nm to 2500 nm at 10 nm intervals, Celsius. The mass has a conical tip (insert of FIG. 4) that
using the black background area of the Leneta card. The contains a thermocouple for local temperature measurement,
Infra Red Re?ectivity Indices Were calculated for each of all of Which is enclosed in an insulated chamber, through
these single-pigment paints folloWing the example method Which only the tip protrudes. This tip is presented to the test
in Table 1 above. Values obtained using this method area media and reacts to the change in temperature that results
shoWn in Table 4. upon contact. The magnitude of the temperature change can
be directly related to the thermal conductivity of the material
by preparation of a calibration curve using Standard mate
TABLE 4 rials With knoWn thermal conductivities. Standards based on
Infrared Re?ectivity Indices for pigments in 30% PVC formulation a) expanded Polystyrene (0.025 W.m_1.K_1), b) Polypropy
lene Homopolymer (0.12 W.m_1.K_1), c) PTFE (0.25 W.m_
Infrared 1.K_1) and d) Calcite single crystal (3.0 W.m_1.K_1) Were
Re?ectivity used as references for these determinations.
Pigment Description Index
Hydrite PXH Water Washed kaolin 0.60
[0060] The standards Were presented to the measuring tip
Rhopaque Opaque polymer spheres 0.90 and the immediate (ie less than 15 seconds) rise in tem
Anatase Titanium dioxide 0.95 perature recorded for each material. The data Was plotted on
Busan 11-M1 Barium metaborate 0.98 a Log-Linear scale for Thermal Conductivity (log scale)
MD 101 Fume silica 0.98 versus Temperature (linear scale) and the line of best ?t
Solar Spectrum 1.00 determined. The formula for this line Was used to determine
Blanc Fixe Micro Barium sulphate 1.00
Scotchlite Spheres Glass spheres 1.01 the corresponding Thermal Conductivities for the Film
Magnum Gloss Precipitated calcium carbonate 1.02 samples for Which temperature rise data Were measured
Resin only control 1.03 using the same procedure. The R2 correlation coefficient for
Rutile Titanium dioxide 1.03 the calibration line thus produced Were found to be excel
Halox Strontium Zinc phosphosilicate 1.04 lent, typically 0.98 or higher. Atypical plot is shoWn in FIG.
MarbleWhite #325 Calcium carbonate 1.05
Omyacarb 10 Calcium carbonate 1.06
3.
Dicalite WB-5 Calcined diatomaceous earth 1.06
Lithopone DS Lithopone 1.07 [0061] It Was found that the value obtained Was in?uenced
Antimony Trioxide Antimony trioxide 1.08 by the mass (or ?lm thickness) of material being measured
Silcosil 125 Silica ?our 1.09 Which is very limited for these thin ?lms. It Was found that
Expancel WB551WE Polymer microspheres 1.09 the temperature rise (related to thermal conductivity)
NeoGen 2000 Calcined clay 1.11 increased With ?lm thickness. In order to obtain comparable
NeoGen FTE Calcined clay 1.12
Satintone W Calcined clay 1.12
values for apparent Thermal Conductivity, measurements
Glomax JDF Calcined clay 1.14 Were made on ?lms cast against siliconiZed release paper at
Nicron 554 Talc 1.23 multiple ?lm thicknesses. Thermal Conductivity Was deter
MetaStar Calcined clay 1.24 mined and plotted against ?lm thickness, alloWing interpo
Alsibronze 39 Mica 1.41 lation of the data to obtain a value for any speci?c ?lm
thickness. Values Were determined for apparent Thermal
Conductivities at ?lm thicknesses of approximately 0.015,
[0057] Extender minerals of the amorphous alumino-sili 0.020, 0.025 and 0.030 inches respectively and are reported
cate, (also knoWn as calcined clay, Whether of the metaka in Table 5 and FIG. 4. The ?lm samples Were removed from
olin or defect spinel form), Mica, Talc have particularly the siliconiZed release paper and temperature rise data
useful infra red re?ectance spectra. For coatings formula determined by presenting these ?lms to the tip of the
tions, these materials should have a mean particle siZe of TC-1000 comparator.
preferably betWeen 0.1 and 20 microns, more preferably
betWeen 0.3 and 10 microns and most preferably betWeen TABLE 5
0.6 and 5 microns, measured by Sedigraph 5100 instrument
(Micromeritics Company). These products may have a Thermal Conductivity measurements on 30% PVC Paint ?lms
broad or narroW particle siZe distribution and may have Thermal Conductivities on 30% PVC Paint Flims (W - m’1 - Kil)
unimodal or polymodal particle siZe distributions, or may
Film Thickness: inch
have different levels of “structure” produced by chemical
and/or thermal processes. 0.015 0.020 0.025 0.030