Thin films with high near-infrared reflectivity deposited on building materials

Abstract

Disclosed are solar-reflective roofing and other building materials having high reflectance of near-infrared radiation and high transmission of radiation in the visible light range and a substantial emissivity so as to reduce the heat island effects experienced by the articles while also maintaining an aesthetically pleasing appearance. Also disclosed are related methods for fabrication of such materials.

Claims

1. A method of fabricating a building material, comprising: applying a plasma to an opaque substrate so as to give rise to a treated region of the substrate; applying a fluid film-forming material to the treated region of the substrate; curing the fluid film-forming material so as to give rise to a thin film; and forming the building material comprising the thin film surmounting the treated region of the substrate, wherein the thin film has a thickness in a range of about 5 nm to about 10 nm; wherein the substrate comprises an asphalt shingle, a roofing membrane, a ceramic roofing tile, painted metal coil stock, a metal shake, a concrete roofing tile, a wood shake, a slate roofing tile, a siding material, a fencing material, a rail material, or a decking material; and wherein the thin film (a) transmits from about 25% to about 80% of radiation having a wavelength of between about 300 nm and about 700 nm, and (b) reflects from about 25% to about 60% of radiation having a wavelength of between about 700 nm and about 2500 nm.

2. The method of claim 1, wherein applying the fluid film-forming material and curing the fluid film-forming material are performed at around atmospheric pressure.

3. The method of claim 1, wherein applying the fluid film-forming material and curing the fluid film-forming material are performed at above atmospheric pressure.

4. The method of claim 1, wherein applying the fluid film-forming material and curing the fluid film-forming material are performed at less than about 100 C.

5. The method of claim 1, wherein the fluid film-forming material comprises tetraethyl orthosilicate.

6. The method of claim 1, wherein the plasma is applied so as to clean a portion of the substrate.

7. The method of claim 1, wherein applying the fluid film-forming material comprises spraying.

8. The method of claim 1, further comprising applying a first gas while applying the fluid film-forming material.

9. The method of claim 1, wherein the substrate comprises a bituminous material.

10. The method of claim 9, wherein a plurality of roofing granules are embedded in the bituminous material prior to applying the plasma to the substrate.

11. The method of claim 1, wherein the thin film comprises a metal oxide.

12. A method of fabricating a building material, comprising: disposing a film-forming material onto an opaque substrate; processing the film-forming material so as to give rise to a thin film surmounting at least a portion of the substrate, wherein processing the film-forming material includes exposing the film-forming material to a plasma, which exposure gives rise to a reactive material forming the thin film; and forming the thin film surmounting at least the portion of the substrate, the thin film having a thickness in a range of from about 5 nm to about 1000 nm, the thin film transmitting from about 25% to about 80% of radiation having a wavelength of between about 300 nm and about 700 nm, and the thin film reflecting from about 25% to about 60% of radiation having a wavelength of between about 700 nm and about 2500 nm.

13. The method of claim 12, wherein the film-forming material is selected so as to provide a building material having an L* of less than about 85.

14. The method of claim 12, wherein the substrate comprises a shingle, a roofing membrane, a shake, a tile, coil stock, or any combination thereof.

15. The method of claim 12, wherein the substrate comprises a plurality of granules disposed atop the substrate prior to disposing the film forming material on the substrate.

16. The method of claim 12, wherein the building material is selected from the group consisting of a roofing material, a siding material, a fencing material, a rail material, or a decking material.

17. The method of claim 12, wherein the substrate, film-forming material, or both are selected such that the building material has an emissivity of at least about 75% for radiation having a wavelength of between about 700 nm and about 2500 nm.

18. The method of claim 17, wherein the substrate, film-forming material, or both are selected such that the building material has an emissivity of at least about 90% for radiation having a wavelength of between about 700 nm and about 2500 nm.

19. The method of claim 12, wherein processing the film-forming material is performed after disposing the film-forming material onto the opaque substrate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The summary, as well as the following detailed description, is further understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings exemplary embodiments of the invention; however, the invention is not limited to the specific methods, compositions, and devices disclosed. In addition, the drawings are not necessarily drawn to scale. In the drawings:

(2) FIG. 1 depicts a schematic view of the operation of the disclosed roofing articles;

(3) FIG. 2 depicts an exemplary, non-limiting sol-gel process for disposing a thin film atop a substrate to give rise to roofing articles according to the present invention; and

(4) FIG. 3 depicts an exemplary, non-limiting plasma-based process for disposing a thin film atop a substrate to give rise to roofing articles according to the present invention.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

(5) The present invention may be understood more readily by reference to the following detailed description taken in connection with the accompanying figures and examples, which form a part of this disclosure. It is to be understood that this invention is not limited to the specific devices, methods, applications, conditions or parameters described and/or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of the claimed invention. Also, as used in the specification including the appended claims, the singular forms a, an, and the include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. The term plurality, as used herein, means more than one. When a range of values is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent about, it will be understood that the particular value forms another embodiment. All ranges are inclusive and combinable.

(6) It is to be appreciated that certain features of the invention which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges include each and every value within that range.

(7) In a first aspect, the present invention provides roofing articles. The disclosed articles suitably include a substrate at least partially surmounted by at least one thin film having a thickness in the range of from about 5 nm to about 5000 nm. The at least one thin film suitably transmits from about 5% to about 100% of radiation having a wavelength of between about 300 nm and about 700 nm, and reflects from about 1% to about 100% of radiation having a wavelength of between about 700 nm and about 2500 nm. The roofing articles also suitably have an emissivity of at least about 75% in the medium-IR (wavelength >2500 nm) range.

(8) A non-limiting, schematic view of a representative article is shown in FIG. 1. As shown, a roofing article made according to the claimed invention is exposed to visible light and NIR radiation. The thin film coating then reflects at least a portion of the NIR radiation. This reflectance of NIR radiation at least partially avoids the heat island effect caused by absorption of NIR radiation, as described elsewhere herein.

(9) The thin film, as shown in FIG. 1, additionally transmits at least a portion of radiation in the visible light range. This in turn enables one observing the roofing article to perceive the underlying color of the article. Such underlying color is suitably black, brown or another color that is aesthetically pleasing to consumers. The net effect of the article is to reduce the previously-described heat island effect and to maintain a temperature T2 on the roof-side of the roofing article that is lower than the temperature T1 on the environment-side of the roofing article where the article is exposed to solar radiation.

(10) As shown in FIG. 1, the inventive articles may include multiple layers of material, including granules, that underlie the thin films. Roofing articles having only single layers of material underlying the thin films are also within the scope of the claimed invention. Thus, substrates may include one or more layers of material. The thin films may reside directly atop the base substrate material (e.g., a bare asphalt shingle), or may reside atop one or more layers, such as paint or sealants, that are disposed atop the base substrate material.

(11) The thin films of the claimed invention may, in some embodiments, have a thickness in the range of from about 10 nm to about 1000 nm. The thin films may even be in the range of from about 20 nm to about 500 nm. Typical thicknesses are between about 20 nm to about 500 nm, although the optimal thickness for a particular embodiment will depend on the needs of the user and will be apparent to those of ordinary skill in the art.

(12) The thin film typically conforms to the surface profile of the substrate, which substrates may include roofing granules or other structures. The film suitably presents an essentially flat surface, as shown in FIG. 1 to the environment exterior to the substrate, although presentation of an essentially flat surface is not always necessary, and the thin film may conform to the surface profile of the underlying substrate.

(13) Granules are typically chemically inert materials, such as mineral particles, and are generally between sand and gravel in size, i.e., between about #8 U.S. mesh and #70 U.S. mesh, and more preferably with sizes ranging from #8 U.S. mesh to #40 U.S. mesh. Preferably, the mineral particles have an average particle size of from about 0.2 mm to about 3 mm, and more preferably from about 0.4 mm to about 2.4 mm.

(14) The thin films of the present invention suitably transmit from about 5% to about 100% of radiation having a wavelength of between about 300 nm and about 700 nm. In some embodiments, the thin films transmit from about 25% to about 100% of radiation having a wavelength of between about 300 nm and about 700 nm, or, in some cases, even from about 50% to about 100% of radiation having a wavelength of between about 300 nm and about 700 nm.

(15) In some embodiments, the at least one thin film transmits radiation having a wavelength of between about 300 nm and about 700 nm essentially uniformly across the range of wavelengths between about 300 nm and about 700 nm. As a non-limiting example, such a thin film according to the present invention transmits radiation having a wavelength of about 350 nm at the same level as radiation having a wavelength of about 550 nm. In such embodiments, roofing articles having multiple colorse.g., a roofing article comprising multiple colored regionsdisplay those colors evenly, such that no one color of the article appears richer or more intense than other colors of that article. In other embodiments, the thin films transmit radiation having a wavelength of between about 300 nm and about 700 nm non-uniformly.

(16) The thin films of the present articles also suitably reflect from about 1% to about 100% of NIR radiation. In some embodiments, the thin films reflect from about 10% to about 45% of NIR radiation, or even from about 30% to about 35% of NIR radiation. The claimed articles preferably reflect at least about 25% of NIR radiation.

(17) The present articles also suitably have an emissivity of from about 75% to about 100% in the middle-IR range, or from about 85% to about 95%, or even of about 90%. Such substantial emissivity enables roofing materials made according to the claimed invention to at least partially avoid the heat island effect that can arise in sunny weather, as described elsewhere herein.

(18) As used in the present specification and claims, L* is a description of the lightness of an article's color, as set forth in the 1976 CIELAB L*a*b* color space, wherein L*=0 signifies black and L*=100 indicates diffuse white, negative values of a* indicate green while positive values indicate magenta, and negative values of b* indicate blue and positive values of b* indicate yellow.

(19) Roofing articles according to the present invention suitably include at least one thin film selected so as to provide a roofing article with an L* value of less than about 85, although in some embodiments, the at least one thin film is selected so as to provide a roofing article with an L* value of less than about 65. The optimal L* for a particular article will be dictated by the needs or preferences of the user.

(20) In some embodiments of the present articles, the L*, a*, and b* values (or some combination thereof) of the thin film match or approximate the corresponding values of the underlying substrate. This may be done in order to optimize the color match between the thin film and the substrate.

(21) Substrates suitable for use in the present articles include shingles, roofing membranes, shakes, tiles, coil stock, and the like. Synthetic and natural substrate materials are both considered suitable for the claimed articles.

(22) Bituminous roofing products used as substrates are considered particularly suitable in the present invention. These materials are typically manufactured in continuous processes in which a continuous substrate sheet of a fibrous material such as a continuous felt sheet or glass fiber mat is immersed in a bath of hot, fluid bituminous coating material so that the bituminous material saturates the substrate sheet and coats at least one side of the substrate. The reverse side of the substrate sheet can be coated with an anti-stick material such as a suitable mineral powder or a fine sand.

(23) Typically, roofing granules are then distributed over selected portions of the top of the sheet, and the bituminous material serves as an adhesive to bind the roofing granules to the sheet when the bituminous material has cooled. The sheet can then be cut into conventional shingle sizes and shapes (such as one foot by three feet rectangles), slots can be cut in the shingles to provide a plurality of tabs for ease of installation and for aesthetic effect, additional bituminous adhesive can be applied in strategic locations and covered with release paper to provide for securing successive courses of shingles during roof installation, and the finished shingles can be packaged. More complex methods of shingle construction can also be employed, such as building up multiple layers of sheets in selected portions of the shingle to provide an enhanced visual appearance, or to simulate other types of roofing products. Alternatively, the sheets can be formed into membranes or roll goods for commercial or industrial roofing applications.

(24) The bituminous material used in manufacturing roofing products is typically derived from a petroleum processing by-product such as pitch, straight-run bitumen, or blown bitumen. The bituminous material can be modified with extender materials such as oils, petroleum extracts, or petroleum residues. The bituminous material can include various modifying ingredients such as polymeric materials, such as SBS (styrene-butadiene-styrene) block copolymers, resins, flame-retardant materials, oils, stabilizing materials, anti-static compounds, and the like. Preferably, the total amount by weight of such modifying ingredients is not more than about 15% of the total weight of the bituminous material.

(25) The bituminous material can also include amorphous polyolefins, up to about 25 percent by weight. Examples of suitable amorphous polyolefins include atactic polypropylene, ethylene-propylene rubber, etc. Preferably, the amorphous polyolefins employed have a softening point of from about 130 C. to about 160 C. The bituminous composition can also include a suitable filler, such as calcium carbonate, talc, carbon black, stone dust, or fly ash, preferably in an amount from about 10 percent to 70 percent by weight of the bituminous composite material. The optimal substrate material for a given application will be apparent to those of ordinary skill in the art.

(26) The thin films of the present invention may include one or more various materials. Metal oxides, and high-index materials are considered suitable thin film materials. The thin films are suitably constructed so as to achieve the desired reflection of NIR (near-IR) radiation while also being sufficiently thin to maintain the desired color of the roofing article.

(27) Suitable metal oxides include, inter alia, titanium oxides, zinc oxides, and zirconium oxides. Suitable combinations of metal oxides and dopants will be apparent to those of ordinary skill in the art; combinations of materials may be selected based on, inter alia, the materials' known transparency to visible light and reflectance of NIR radiation.

(28) High refractive index materials are suitable for use in the thin films of the claimed articles. Such materials are typically chosen on the basis of the high optical index contrast between air and such materials. As non-limiting examples, TiO.sub.2 and Fe.sub.2O.sub.3 are considered suitable high-index materials. Other high-index materials, will be known to those of ordinary skill in the art. TiO.sub.2 (n.sub.anastase=2.55 at =590 nm; n.sub.rutile=2.903 at =590 nm) is considered especially suitable, on the ground that it has a particularly high refractive index and, at certain thicknesses, is essentially transparent in visible light.

(29) Suitable high-index materials include those materials having a refractive index of at least about 1.5, at least about 2, or even greater. A number of metal oxides, minerals, and the like possess such an index and will be easily identified by those of ordinary skill in the art.

(30) The roofing articles may also include sealants, adhesives, binders, and other materials that are useful in assembling such articles or in maintaining the structural integrity of the articles. For example, the roofing articles may include one or more sealants to enhance the attachment of the thin film or films to the underlying substrate. As a non-limiting example, a sealant may be applied to an asphaltic substrate before application of the thin film so as to prevent diffusion of the materials in the thin film. Plastic substrates may also contain plasticizers or other additives to enhance their performance.

(31) Algaecides, biocides, and other active agents may also be included in the claimed articles. The thin film may itself be selected to provide additional properties such as hydrophilic properties, photocatalytic effects, e.g., for self-cleaning, inhibition of microbial growth, or the like, to the roofing article.

(32) The roofing articles may also include colorants, pigments, dyes, and the like. These additional components may be employed to enhance the aesthetic appeal of the roofing articles or to enhance the articles' performance.

(33) Clear or colored coatings may, as desired, also be incorporated into the roofing articles. As one non-limiting example, a polymeric coating may be disposed atop at least a portion of a roofing article so as to provide mechanical or structural stability to the article and also impart chemical stability or weatherability. A non-limiting list of such coatings includes poly(meth)acrylates, polyurethanes, fluoropolymers, phosphates, titanates, zirconates, silicates such as metal silicates, silicas, and other polymers. Such coatings are applied by methods such as spraying, sonic spraying, ink jet printing, roll coating, curtain coating, or by extrusion coating. Other application methods will be known to those of ordinary skill in the art.

(34) As described elsewhere herein, the roofing articles may include multiple thin film layers. The thin film layers may be of the same or different materials, and the optimal combination of thin films and thin film materials will dictated by the user's needs.

(35) Also provided are methods of fabricating solar-reflective building materials, including roofing articles, decking, rails, siding, fencing, and the like. The disclosed methods include providing a substrate having an upper surface and disposing onto at least a portion of the upper surface of the substrate at least one thin film having a thickness in the range of from about 5 nm to about 5000 nm.

(36) The at least one thin film suitably transmits from about 5% to about 100% of radiation having a wavelength of between about 300 nm and about 700 nm, and reflects from about 1% to about 100% of radiation having a wavelength of between about 700 nm and about 2500 nm. The thin films and processing conditions are suitably selected such that the resultant roofing articles suitably have an emissivity of at least about 75% in the medium-IR (wavelength >2500 nm) range, which allows for roofing articles that at least partially avoid the heat island effect described elsewhere herein.

(37) The at least one thin film is suitably disposed onto the upper surface of the substrate by spraying, sol-gel spraying, electrospraying, chemical vapor deposition, or by plasma-enhanced chemical vapor deposition. Laminating, sputtering, electroplating, electroless plating, thermal spraying, physical vapor deposition, and plasma-assisted physical vapor deposition are also considered suitable deposition methods. Methods of applying thin films to other substrates, such as glass, are known in the art.

(38) One exemplary, non-limiting deposition process according to the claimed invention is shown in FIG. 2. In that figure, a conveyor belt transports a substrate to a plasma source, where the plasma acts to prepare the surface for sol-gel deposition of the thin film.

(39) The substrate is next transported to a spray cabin, wherein a liquid formulation of the thin film material is applied, e.g., by spraying, to the substrate. The material is then dried, e.g., with infrared radiation, or otherwise treated or cured to give rise to a thin film having the desired thickness. The process is suitably performed at about atmospheric pressure and at or below about 100 C., or even below about 80 C., although higher temperatures may be suitable.

(40) FIG. 3 depicts an alternative, non-limiting process for plasma-based deposition of a thin film to a substrate. As shown in that figure, a conveyor transports the substrate to a confined zone. Within the confined zone, the substrate is then controllably exposed to a fluid or gase.g., air, nitrogen, oxygen, and the likealong with a film-forming material.

(41) In the example of FIG. 3, the film-forming material is tetraethyl orthosilicate (TEOS), although other materials are within the scope of the claimed invention. Within the confined zone, the gas and film-forming material are exposed to a plasma source, which exposure gives rise to a reactive material forming a thin film of the desired thickness. The process is suitably performed at about atmospheric pressure. As further shown in FIG. 3, excess reactive materials and gases may be extracted from the confining system.

(42) In some embodiments, disposition of the thin film onto the upper surface of the substrate is performed at less than about 200 C. In other embodiments, the disposition is performed at less than about 100 C., or even at less than 80 C. Disposition at temperatures of less than about 80 C. is preferable, for example, where the substrate is bituminous or asphaltic in nature and may not be capable of extended exposure to higher temperatures.

(43) Disposition is also suitably performed at about or greater than atmospheric pressure, although deposition at reduced pressures is contemplated. Atmospheric or increased-pressure deposition is typically employed where the substratee.g., an asphaltic shinglemay be adversely impacted by reduced pressure or vacuum.

(44) The thin films of the present process suitably have a thickness in the range of from about 10 nm to about 1000 nm, or from 5 nm to about 750 nm, or even from about 20 nm to about 500 nm. As described elsewhere herein, the optimal thickness will depend on the needs of the user and the desired durability or mechanical strength of the finished article; typical articles have thin films with a thickness in the range of from 20 nm to about 500 nm.

(45) The thin films suitably transmit from about 25% to about 100% of visible light radiation. Thin films that transmit from about 50% to about 100% of visible light radiation, or even from about 75% to about 100% of visible light radiation are also suitable.

(46) As described elsewhere herein, the thin films suitably transmit visible light radiation essentially uniformly across the wavelength range of from about 300 nm to about 700 nm. In some embodiments, the thin films are chosen to as to transmit visible light radiation in a non-uniform manner across the wavelength range of from about 300 nm to about 700 nm.

(47) The thin films of the present articles also suitably reflect from about 1% to about 100% of NIR radiation. In some embodiments, the thin filmsor the articles as a wholereflect from about 10% to about 45% of NIR radiation, or even from about 30 to about 35% of NIR radiation. The articles preferably reflect at least about 25% of NIR radiation.

(48) The articles also suitably have an emissivity of from about 75% to about 100% in the middle-IR range, or from about 85% to about 95%, or even of about 90%. Such substantial emissivity enables roofing materials made according to the claimed invention to at least partially avoid the heat island effect that can arise in sunny weather, as described elsewhere herein.

(49) As described elsewhere herein, the thin films of the present process are typically selected so as to provide a finished article having a L* value of less than about 85, or even a L* value of less than about 65. The a*, b*, L*, or any of these values the thin film may be matched to the corresponding value or values of the substrate, as described elsewhere herein.

(50) The provided processes are suitably applied to a variety of substrates, including shingles, roofing membranes, shakes, tiles, coil stock, and the like. Asphaltic and bituminous substrate materials are considered suitable substrate materials for the present invention, under appropriate process conditions. In some embodiments, the substrate or the thin film includes an adhesive or sealant to bond the substrate and film together. In other embodiments, an adhesive or sealant is disposed between the film and substrate to bond the two.

(51) Materials suitable for the thin films of the disclosed processes are described elsewhere herein. Such materials include, inter alia, metal oxides, and high-index materials.

(52) The disclosed processes also include application of a sealant, a binder, an adhesive, a biocide, an algaecide, and the like to the substrate, to the thin film, or to both to improve the mechanical or structural properties of the finished article. Clear or protective coatings may also be applied to the finished articles to provide additional desirable properties or durability to the finished articles. Methods of applying such coatings include spraying and the like; the optimal method for applying coatings will be apparent to those of skill in the art.

(53) Where warranted, the claimed methods also include preparation of the substrate surface before disposition of the thin film atop the substrate. Such preparation may include, e.g., cleaning the substrate by washing, pressure washing, steam cleaning, and the like. Excess granules and foreign matter are typically removed before application of the thin films.

(54) The claimed invention is not limited to roofing materials, and includes a variety of opaque building materials that, in some cases, are used on building exteriors. Such materials suitably include roofing materials as well as siding materials, fencing materials, rail materials, decking materials, and the like.

(55) The materials suitably include a substrate at least partially surmounted by at least one thin film having a thickness in the range of from about 5 nm to about 5000 nm. The film can be from about 100 to about 1000 nm in thickness, from 200 to about 500 nm in thickness, or even about 200 nm in thickness.

(56) The thin film suitably transmits in the range of from about 5% to about 100% of radiation having a wavelength of between about 300 nm and about 700 nm in some embodiments. Films that transmit from about 20% to about 80% of such radiation, or even from about 35% to about 65% of such radiation are also suitable.

(57) The thin film also suitably reflects from about 1% to about 100% of radiation having a wavelength of between about 700 nm and about 2500 nm. In some embodiments, the thin film reflects from about 20% to about 80% of such radiation, from about 35% to about 65% of such radiation, or even about 50% to about 60% of such radiation.

(58) The article as a whole may also be configured to reflect from about 1% to about 100% of radiation having a wavelength of between about 700 nm and about 2500 nm, or from about 20% to about 80% of such radiation, from about 35% to about 65% of such radiation, or even about 50% to about 60% of such radiation.

(59) The materials also suitably have an emissivity of at least about 75% for radiation having a wavelength of greater than about 2500 nm. In some embodiments, the emissivity is at least about 85%, 90% or even at least about 95% for such radiation.

Examples and Non-Limiting Embodiments

(60) In one, non-limiting embodiment of the present invention, films of TiO.sub.2 were deposited by spraying directly on shingles measuring 3 inches3 inches by spraying various amounts of sol onto the shingles to form reflective coatings.

(61) The sol was synthesized by adding 15.22 mL of titanium tetrabutoxide (Aldrich, www.sigmaaldrich.com, St. Louis, Mo., USA) in a drop-by-drop fashion to a mixture of 2.24 mL of acetyl acetone (VWR Prolabo, www.fr.vwr.com, France) and 62.54 mL of isopropanol. The resulting mixture was then stirred for one hour. The resulting final TiO.sub.2 dry contenti.e., weight percentage of TiO.sub.2 in the solwas 10%.

(62) The resulting articles were then exposed to solar radiation and their reflectance was monitored using the ASTM C-1549 method using a portable solar reflectometer (Devices & Services, Dallas, Tex., USA). The solar reflectance percentage (SR) results achieved by this sol coating onto the described shingles were as follows:

(63) TABLE-US-00001 sol amount SR (%) L* a* b* reference - 8 33.9 0.7 7.1 shingle 2 mL 13 42.3 0.2 6.2 4 mL 15 45.3 0.4 7.5 6 mL 16 46.1 0.9 9.5