Patent Application
20230416099
The present invention relates to a precursor material for a silica wet gel and methods of making silica wet gel. The present invention also relates to silica wet gel and methods of making silica wet gel. The present invention also relates to silica aerogel and methods of making silica aerogel. Additionally, the present invention relates to silica aerogel sheets and methods of making silica aerogel sheets. Further, the present invention relates to an article having a glass sheet and a silica aerogel sheet and methods of making such an article. Still further, the present invention relates to an insulating glazing unit having a silica aerogel sheet between glass sheets and methods of making such an insulating glazing unit. Further yet, the present invention relates to a laminated glass assembly having a silica aerogel sheet between glass sheets and methods of making such a laminated glass assembly.
Silica aerogels are thermally insulating materials, but traditionally they have had limited applications in windows and other glazings because they have not traditionally achieved the right combination of mechanical, thermal and optical properties to be fully acceptable for all such applications. Researchers have experimented with many different precursor recipes and methods in the hope of producing silica aerogel with an optimum combination of mechanical, thermal and optical properties but have been unsuccessful. While some recipes and methods led to certain properties being optimized, other properties were compromised.
It would be desirable to provide a precursor material, silica wet gel, silica aerogel and methods of making such materials that can be used to form an enhanced silica aerogel sheet having a desirable combination of mechanical, thermal and/or optical properties. It would be particularly desirable to provide silica aerogel that has high visible transmission and low haze. Further, it would be desirable to provide an article comprising a glass sheet and an enhanced silica aerogel sheet. It would also be desirable to provide an insulating glazing unit comprising an enhanced silica aerogel sheet. Similarly, it would be desirable to provide a laminated glass assembly comprising an enhanced silica aerogel sheet. It would also be desirable to provide methods of making high quality silica aerogel that are commercially feasible and do not require expensive or excessive processing.
Certain embodiments include a method of making a silica aerogel. The method comprises steps of (a) synthesizing a silica wet gel from methyl silicate 51, (b) aging the silica wet gel for an aging time period until structural changes of the silica wet gel no longer occur, (c) subjecting the silica wet gel to solvent extraction with methanol for an extraction time period, and (d) drying the silica wet gel to form a silica aerogel having a linear shrinkage value of 3% or less (e.g., 2.7% or less), a visible transmission greater than 98% and a haze value of 2.5% or less (e.g., 2.0% or less or 1.5% or less). In some cases, the step of drying the silica wet gel forms the silica aerogel such that less than 3% (e.g., less than 2.0%) methanol remains within the silica aerogel. Also, in some cases, the step of drying the silica wet gel forms the silica aerogel with a maximum resilience at complete breaking point of greater than 300 J/m3 (e.g., greater than 400 J/m3). In some cases, the aging step comprises aging the silica wet gel at room temperature. Further, the aging time period can be at least 7 days (168 hours). Also, the extraction time period can be less than 24 hours.
In some embodiments, the step of synthesizing the silica aerogel from methyl silicate 51 comprises steps of (a) preparing a first solution by mixing methyl silicate 51 and methanol, (b) preparing a second solution by mixing ammonium hydroxide and water, (c) mixing the first solution and the second solution together to form a precursor material, and (d) allowing components in the precursor material to react to form silica wet gel. The precursor material can have a weight percent ratio of the methyl silicate 51:water of between 0.25:1 and 2:1, such as a weight percent ratio of the methyl silicate 51:water of between 0.5:1 and 1:1.
Other embodiments provide a silica aerogel synthesized from methyl silicate 51. The silica aerogel can have a visible transmission of at least 98% and a haze value of 2.5% or less, and further includes at least one of the following features (A) through (E):
Additionally, the silica aerogel can be prepared by a method comprising the steps of: (a) preparing a first solution by mixing methyl silicate 51 and methanol, (b) preparing a second solution by mixing ammonium hydroxide and water, (c) mixing the first solution and the second solution together to form a precursor material, (d) allowing components in the precursor material to react to form silica wet gel, (e) aging the silica wet gel for an aging time period until structural changes of the silica wet gel no longer occur, (f) subjecting the silica wet gel to solvent extraction with methanol for an extraction time period, and (g) drying the silica wet gel to form the silica aerogel. The precursor material can have a weight percent ratio of the methyl silicate 51:water of between 0.25:1 and 2:1, such as a weight percent ratio of the methyl silicate 51:water of between 0.5:1 and 1:1. In some cases, the step of drying the silica wet gel forms the silica aerogel with a linear shrinkage value of 2.7% or less.
The following detailed description is to be read with reference to the drawings, in which like elements in different drawings have like reference numerals. The drawings, which are not necessarily to scale, depict selected embodiments and are not intended to limit the scope of the invention. Skilled artisans will recognize that the examples provided herein have many useful alternatives that fall within the scope of the invention.
In the present specification, anywhere the terms “comprising” or “comprises” are used, those terms have their ordinary, open-ended meaning. In addition, the disclosure at each such location is to be understood to also disclose that it may, as an alternative, “consist essentially of” or “consist of.”
Applicant has observed that silica aerogels having lower haze still may suffer from other undesirable optical defects. One common optical defect is the appearance of optical distortion lines caused by structural non-uniformities within the silica aerogel. Applicant has noted that as haze is reduced in the silica aerogel, optical distortion lines may become more visible. Applicant developed silica wet gels that can be used to form enhanced silica aerogels, such as silica aerogel sheets, having few to no optical distortion lines while also maintaining other desirable properties. Applicant has also developed methods of making silica aerogels, such as silica aerogel sheets, that have desirable properties. Preferably, the silica aerogel sheets are devoid of structural non-uniformities that create optical distortion lines visible to the naked eye. The enhanced silica aerogel sheets can achieve an exceptional, surprising combination of optical, thermal and/or mechanical properties, which makes them highly advantageous for use in window applications.
Certain embodiments provide a precursor material for silica wet gel. The precursor material comprises a silica precursor, such as silicon alkoxide or alkoxysilane. The precursor material serves as an intermediate product that is used to form silica wet gel. The term “silica wet gel” refers to a material that is obtained by allowing components of a precursor material including silicon alkoxide to react to form a wet gel. Further, the term “silica aerogel” refers to a material that is obtained by removing liquid from a silica wet gel and replacing the liquid with a gas or vacuum.
In some embodiments, the precursor material comprises (or consists essentially of or consists of) silicon alkoxide, solvent, water and base catalyst. The silicon alkoxide, solvent, water and base catalyst are provided within selected weight percent ranges. Applicant has identified a “sweet spot” of weight percent ranges for the precursor material that can be used to form silica wet gel, which in turn can be used to form silica aerogel having a surprising combination of optical, mechanical and/or thermal properties.
Several reactions take place during silica wet gel synthesis: hydrolysis, condensation, nucleation and growth. These various reactions can have different reaction rates depending on the components used for the precursor material. The reaction rates affect mechanical, thermal and optical properties of a resulting silica aerogel. Thus, the resulting aerogel is highly sensitive to variations in precursor material components and percentage of components. As an example, the hydrolysis reaction rate is determined by the amount of catalyst in the precursor material. The hydrolysis reaction is also exothermic, so it imparts heat to the precursor material, which in turn accelerates the condensation reaction rate. As a consequence, too much catalyst can accelerate the condensation reaction rate. Accelerated condensation reaction rates are undesirable since they can lead to an accelerated nucleation rate and an accelerated growth rate. Furthermore, if the growth rate exceeds the nucleation rate, the three-dimensional polymer structure will have unduly large particle sizes. Larger particle sizes create more scattering of light, which in turn leads to undesirable properties such as increased haze and reduced visible transmission. All of these variabilities make silica wet gel and aerogel synthesis unpredictable.
In some embodiments, the precursor material comprises silicon alkoxide, solvent, water and catalyst. Applicant has identified a “sweet spot” of weight percentage ranges for these components. In certain cases, the precursor material comprises (or consists essentially of or consists of) silicon alkoxide at a weight percent greater than or equal to 15% and less than or equal to 24%, solvent at a weight percent of greater than or equal to 60% and less than or equal to 68%, water at a weight percent of greater than or equal to 15% and less than or equal to 17%, and catalyst at a weight percent of greater than or equal to 0.08% and less than or equal to 0.2%. In certain cases, the silica wet gel material comprises (or consists essentially of or consists of) silicon alkoxide precursor at a weight percent greater than or equal to 15.28% and less than or equal to 19%, solvent at a weight percent of greater than or equal to 65.16% and less than or equal to 68.52%, water at a weight percent of greater than or equal to 15.68% and less than or equal to 16.04%, and catalyst at a weight percent of greater than or equal to 0.15% and less than or equal to 0.17%.
Also, in some embodiments, the silica wet gel has a specified weight percent ratio of silicon alkoxide precursor:water. Applicant has also identified a ratio range for the silicon alkoxide precursor and water in the silica wet gel that can be used to form silica aerogel having desired and unexpected properties. In some cases, the silica wet gel has a weight percent ratio of the silicon alkoxide precursor: water of between 0.25:1 and 2:1, such as a weight percent ratio of the silicon alkoxide precursor:water of between 0.5:1 and 1:1.
In some cases, the precursor material comprises methyl silicate 51 as the silicon alkoxide. Applicant has found that methyl silicate 51 provides desirable results. Applicant has discovered that by using methyl silicate 51 as the silicon alkoxide, the resulting silica aerogel has less haze and less optical distortion than with other silicon alkoxides. Applicant has found that MS-51 provides desirable results because it is pre-hydrolyzed. As a result, a hydrolysis reaction in the precursor material is absent, which leads to a lower condensation rate and thus a lower nucleation rate. Lower nucleation rates allow the formation of a three-dimensional polymer structure with smaller particle sizes. The resulting silica aerogel therefore has less scattering of light and therefore reduced haze and increased transmissivity. For commercial window applications, aerogel particle size is desirably less than 5 nm to have the lowest possible light scattering and thus acceptable haze and transmissivity.
Further, in some embodiments, the precursor material has a weight percent ratio of the methyl silicate 51:water of between 0.25:1 and 2:1, such as a weight percent ratio of the methyl silicate 51:water of between 0.5:1 and 1:1. Applicant has discovered that precursor materials having methyl silicate 51:water within the listed weight percent ratios can be used to form silica wet gels and therefore silica aerogels materials having numerous desirable and unexpected properties.
Also, in some cases, the precursor material comprises methanol as the solvent. Applicant has discovered that by using methanol as the solvent, the resulting silica aerogel has less haze and less optical distortion than with other solvents.
In certain cases, the precursor material comprises ammonium hydroxide as the catalyst. Here too, Applicant has discovered that by using ammonium hydroxide as the catalyst, the resulting silica aerogel has less haze and less optical distortion than with other catalysts.
In some embodiments, the precursor material comprises (or consists essentially of or consists of) methyl silicate 51, methanol, water and ammonium hydroxide. In certain cases, the precursor material comprises (or consists essentially of or consists of) methyl silicate 51 at a weight percent of greater than or equal to 15% and less than or equal to 24%, methanol at a weight percent of greater than or equal to 60% and less than or equal to 68%, water at a weight percent of greater than or equal to 15% and less than or equal to 17%, and ammonium hydroxide at a weight percent of greater than or equal to 0.08% and less than or equal to 0.2%. Furthermore, in certain cases, the precursor material comprises (or consists essentially of or consists of) methyl silicate 51 at a weight percent of greater than or equal to 15.28% and less than or equal to 19%, methanol at a weight percent of greater than or equal to 65.16% and less than or equal to 68.52%, water at a weight percent of greater than or equal to 15.68% and less than or equal to 16.04%, and ammonium hydroxide at a weight percent of greater than or equal to 0.15% and less than or equal to 0.17%.
Other embodiments provide a method of making a silica wet gel.
In certain cases, step 205 comprises preparing a first solution by mixing methyl silicate 51 and methanol and step 210 comprises preparing a second solution by mixing ammonium hydroxide and water. Further, step 215 comprises mixing the first solution and the second solution together to form a precursor material having components within specific weight percentages.
In some cases, the first solution comprises (or consists essentially of or consists of) methyl silicate 51 at a weight percent of greater than or equal to 15% and less than or equal to 30% and methanol at a weight percent of greater than or equal to 60% and less than or equal to 90%. Furthermore, in some cases, the second solution comprises (or consists essentially of or consists of) ammonium hydroxide at a weight percent of greater than or equal to 0.5% and less than or equal to 1.0% and water at a weight percent of greater than or equal to 99% and less than 100%.
In some cases, the precursor material has a weight percent ratio of the methyl silicate 51:water of between 0.25:1 and 2:1, such as between 0.5:1 and 1:1. Also, in some cases, the precursor material is devoid of N,N-dimethylformamide. This can optionally be the case for the precursor material in any embodiment of the present disclosure.
Other embodiments provide a method of making silica aerogel.
Generally, the aging step 222 includes keeping the silica wet gel in an airtight environment for a selected period of time. Applicant has found that the aging process allows structural transformation to occur in the three-dimensional particles polymeric structure of the silica wet gel that enhance the mechanical strength of the structure. One exemplary significant structural transformation that takes place during aging is a decrease in spherical silica particle diameter. Another exemplary structural transformation is a decrease in pore size. Pore size is a size of pore spaces between spherical silica particles. Pore sizes are often recorded in terms of average pore size. Another exemplary structural transformation is a strengthening of the necking point between two spherical silica particles. The necking point is the point where two adjacent spherical silica particles adjoin.
The selected time period is a time period in which the aging process reaches saturation. Once saturation has occurred, no further structural transformation of the wet gel occur. Applicant has discovered that optimal properties are obtained when the selected time period is a time period of at least 7 days (168 hours), at least 8 days (192 hours), at least 9 days (216 hours) or at least 10 days (240 hours). Additionally, warping of the silica wet gel often takes place during subsequent processes. For example, in many cases, silica wet gel shrinks during drying. However, Applicant has found that a time period of at least 7 days helps prevent warping such as shrinking.
In certain embodiments, the silica wet gel is dried in step 225 using a conventional aerogel drying method. In many cases, the silica wet gel is placed in either a freeze dryer, a supercritical dryer, or an ambient dryer. In such instances, the step 225 of drying the silica wet gel comprises either a freeze-drying process, a supercritical drying process, or an ambient drying process.
In some cases, the silica wet gel is dried using a supercritical drying method (also known as critical point drying). As is well-known to skilled artisans, supercritical drying involves a solvent exchange. The silica wet gel is placed in a solvent bath so that water initially inside the silica wet gel is replaced with the solvent in the bath.
The silica wet gel is then placed in a pressure vessel along with liquid carbon dioxide. The pressure vessel may be filled with, and emptied of, liquid carbon dioxide multiple times, so as to remove the organic solvent and leave liquid carbon dioxide in its place. The liquid carbon dioxide is then heated past its critical temperature and pressure and removed, thereby leaving silica aerogel.
One drawback with past supercritical drying methods is that higher residual solvent often remains in the silica aerogel after drying. Another drawback is that shrinkage occurs as the silica wet gel dries to form silica aerogel. Residual solvent and shrinkage can compromise the resulting optical, mechanical and thermal properties of the resulting silica aerogel.
Applicant has discovered surprising results when using methanol as the solvent in the solvent exchange. By using methanol as the solvent, the resulting silica aerogel has less haze and less optical distortion than with other solvents. Further, methanol leads to fewer residual solvent and less shrinkage of the silica aerogel after drying.
In certain embodiments, the silica wet gel can be placed in a methanol solvent bath for 8 hours, removed and then placed in another methanol solvent bath for 8 more hours. The total time period in which the hydrophilic silica wet gel is in the solvent bath can be less than 20 hours, such as less than 17 hours. This is desirable as longer solvent processing time can lead to deterioration in optical properties. Additionally, a shorter solvent processing time is advantageous for commercial production.
In other cases, the silica wet gel is dried using an ambient drying method. As used herein, ambient drying involves drying the flexible gel layer under ambient conditions (e.g., at a temperature in a range of from about 50 degrees to about 85 degrees Fahrenheit, and more typically in a range of from 68 degrees to 72 degrees Fahrenheit). The liquid in the silica wet gel is allowed to slowly evaporate under controlled conditions, leaving silica aerogel. The controlled conditions ensure that the evaporation is slow enough so that the silica network of the gel does not collapse during the drying. With ambient drying, the dryer is configured to establish a controlled environment in its interior. This may involve a controlled temperature, a controlled pressure, a controlled airflow, a controlled humidity, or any combination thereof.
In still other cases, the silica wet gel is dried using a freeze-drying method. The silica wet gel is frozen and then put into a vacuum chamber. The solvent is then removed to leave silica aerogel. Any suitable freeze-drying technique known in the art may be used. As non-limiting examples, the silica wet gel can be placed into a household freezer, liquid nitrogen, or in a cryogenic mixture (e.g., a dry-ice/solvent mixture, such as a dry-ice and acetone bath).
Other fabrication techniques can be used such a rapid supercritical extraction technique. Reference is made to U.S. Pat. No. 8,080,591, the salient teachings of which are incorporated herein by reference.
In some cases, the silica aerogel is provided in the form of a silica aerogel sheet. This is in contrast to aerogel in flowable granular or otherwise particulate form. The aerogel sheet is preferably self-supporting, i.e., once fully synthesized and formed, the sheet can retain sheet form without being adhered to glass or another support. This can optionally be the case for any embodiment of the present disclosure involving a silica aerogel sheet.
Certain embodiments provide a method of making a silica aerogel sheet.
The silica aerogel sheet is an enhanced sheet having desirable and unexpected properties. First, the silica aerogel sheet desirably has low haze. For any embodiment involving a silica aerogel sheet, the haze can optionally be less than 2.5%, such as less than 2%. In some cases, the silica aerogel sheet has a haze of less than or equal to 1.75%. This preferably is the case for any embodiment involving a silica aerogel sheet. Haze can be measured in well-known fashion, e.g., using a BYK HazeGard plus instrument. Reference is made to ASTM D 1003-00: Standard Test method for Haze and Luminous Transmittance of Transparent Plastics, the contents of which are incorporated herein by reference.
Further, the silica aerogel sheet desirably has few to no optical distortion lines (“ODL”). After observing the appearance of ODL in sheets from various silica aerogels, Applicant developed a method for assessing severity of ODL that involves calculating a global structural similarity index measure (“SSIM”) for a silica aerogel sheet sample.
The ODL is assessed in the following manner. First, a silica aerogel sheet sample 500 is provided. The sheet sample 500 has a size of 5×5 inches. The silica aerogel sheet sample 500 is placed between a light source 510 and a projection screen 520. Reference is made to
The light source 510 is a full spectrum LED with eight individual white light bulbs replicating a daylight spectrum. One suitable light source 510 is a fiber-coupled cold white LED (model number MCWHF2k) obtained from Thorlabs Inc. (a company having its headquarters in Newton, New Jersey, U.S.A.). When light from the light source 510 passes through the sheet sample 500, a projection 530 of the sample is provided on the projection screen 520. Any optical distortion shows up on the projection 530 as a shadow (i.e., a shadow projection).
A DSLR camera 540 is placed at a distance D3 of 14 inches from a center point of the projection screen 520, aimed at the distortion image 530, and at an angle of 70 degrees from a line perpendicular to the sightline axis. One suitable DSLR camera 540 is a Canon Powershot SX540HS, 20.3 MegaPixel 1/2.3 in CMOS sensor with a 4.3-214 mm zoom lens obtained from Canon USA (a company having its headquarters in Melville, New York, U.S.A.).
The optical zoom on the camera 540 is adjusted to capture a window of an image of the shadow projection 530 at the highest resolution possible. This captured image is the distortion image. Note that because the camera 540 is at an angle to the projection screen 520, the shadow projection 530 is slightly trapezoidal (similar to the keystone effect in projectors). The distortion image therefore captures the largest rectangular window that can be cropped from the shadow projection 530.
Likewise, the optical zoom on the camera 540 is adjusted to capture a window of an image of the projection screen 520 alone (i.e., without the shadow projection 530) at the highest resolution possible. This captured image is the reference image. The reference image captures the same size window that is captured for the distortion image.
Next, a global SSIM is calculated by comparing the distortion image to a reference image. The global SSIM is a measure of the total differences between the distortion image and the reference image. The present invention uses the method described in Z. Wang, A. C. Bovik, H. R. Sheikh and E. P. Simoncelli, “Image quality assessment: From error visibility to structural similarity,” IEEE Transactions on Image Processing, vol. 13, no. 4, pp. 600-612, April 2004, the entire contents of which are incorporated herein by reference. The global SSIM is calculated using the following formula:
with:
Further, the global SSIM can be calculated using a software program or index calculating code. For example, the global SSIM can be calculated using a Matlab implementation of the SSIM index disclosed at https://ece.uwaterloo.ca/˜z70wang/research/ssim/#usage, the entire contents of which are incorporated herein by reference.
The calculated global SSIM ranges from 0.00 to 1.00, with 0.00 showing the lowest structural similarity and 1.00 showing the highest structural similarity. Applicant has discovered that silica aerogel sheets produced from recipes described herein provide distortion images with a global SSIM of greater than 0.80. Applicant has discovered that sheets having a global SSIM of greater than 0.80 advantageously provide low ODL. Moreover, Applicant has discovered that these particular recipes surprisingly do so without being substantially sensitive to the drying process or other downstream processes used to form the silica aerogel sheet.
Thus, in some cases, the silica aerogel sheet has a calculated global SSIM of greater than This can optionally be the case for any embodiment of the present disclosure involving a silica aerogel sheet. In particular cases, the silica aerogel sheet can have a calculated global SSIM of greater than 0.82, greater than 0.85, greater than 0.87, greater than 0.90, greater than greater than 0.92 or greater than 0.93. In preferred cases, the silica aerogel sheet is devoid of structural non-uniformities that create optical distortion lines visible to the naked eye. In addition, the distortion image produced for such a silica aerogel sheet preferably is also devoid of optical distortion lines visible to the naked eye. This is preferably the case for any embodiment involving a silica aerogel sheet, optionally in combination with a visible transmission in the range noted in the next paragraph.
The silica aerogel sheet desirably has high visible transmission. In some cases, the silica aerogel sheet has a visible transmission of greater than 98%. The term “visible transmission” is well known in the art and is used herein in accordance with its well-known meaning to refer to the percentage of all incident visible radiation that is transmitted through an object (e.g., through the aerogel sheet 300). Visible radiation constitutes the wavelength range of between about 380 nm and about 780 nm. Visible transmission, as well as visible reflection, can be determined in accordance with NFRC 300-2017, Standard Test Method for Determining the Solar and Infrared Optical Properties of Glazing Materials and Fading Resistance of Systems. The well-known and commercially available LBNL WINDOW 7.4 computer program can be used in calculating these and other reported optical properties.
The silica aerogel sheet can also have desirable transmitted color characterized by “a” and “b” color coordinates that are each between −2 and 2. This can optionally be the case for any embodiment of the present disclosure involving a silica aerogel sheet, preferably in combination with visible transmission and haze levels in the ranges noted above. The present discussion of color properties is reported using the well-known color coordinates of “a” and “b.” In more detail, the color coordinates are indicated herein using the subscript h (i.e., an and bn) to represent the conventional use of the well-known Hunter Lab Color System (Hunter methods/units, Ill. D65, 10 degree observer). The present color properties can be calculated as specified in “Insight on Color,” “Hunter L, a, b Color Scale,” Applications Note, Vol. 8, No. 9, June 2008 (2008), the relevant teachings of which are incorporated herein by reference.
In addition, the silica aerogel sheet can have a low bulk density. In certain embodiments, the silica aerogel sheet has a bulk density of less than 150 mg/cc. In some cases, the silica aerogel sheet has a bulk density of less than 140 mg/cc, such as less than 130 mg/cc, or even less than 125 mg/cc. In certain embodiments, the silica aerogel sheet has a bulk density of higher than 70 mg/cc. In some cases, the silica aerogel sheet has a bulk density of higher than 80 mg/cc, such as higher than 85 mg/cc, or even higher than 95 mg/cc. In preferred embodiments, the silica aerogel sheet has a bulk density of between 100 mg/cc and 150 mg/cc, such as 120 mg/cc. The density of the silica aerogel sheet can optionally be in this range for any embodiment of the present disclosure, preferably in combination with visible transmission and haze levels in the ranges noted above (e.g., Tvis greater than 98% together with haze of less than 2.5%, less than 2%, or less than 1.75%). Bulk density is calculated by weighing the aerogel sheet and then calculating the volume using the weight along with the dimensions of the aerogel sheet.
The silica aerogel sheet can also have low thermal conductivity. For example, the silica aerogel sheet can have a thermal conductivity of less 20 mW/m*K, such as less than 13 mW/m*K in air (or less than 10 mW/m*K in inert gas such as argon). The thermal conductivity of the silica aerogel sheet can optionally be in one or both of these ranges for any embodiment of the present disclosure. Thermal conductivity can be determined using a conventional heat flow meter, such as the well-known TA Instruments Fox 200 heat flow meter, which is commercially available from Waters Corporation (New Castle, Delaware, U.S.A.).
Further, the silica aerogel sample can have a flexural modulus of less than 750 kPa and perhaps less than or equal to 720 kPa, 700 kPa, 680 kPa or 650 kPa. The flexural modulus of a material is a mechanical property that measures a material's stiffness or resistance to bending and is defined as the ratio of stress to strain in flexural deformation. It is determined from the slope of a stress-strain curve produced by a flexural test on an aerogel sample having dimensions of 74.5 mm in length, 14.5 mm in width and 3.2 mm in thickness. The flexural test is performed in accordance with ASTM D790: Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Material, the contents of which are incorporated herein by reference. The higher the flexural modulus of a material, the harder it is to bend. Conversely, the lower the flexural modulus, the easier it is for the material to bend under an applied force.
Even further, the silica aerogel sheet can have an average pore size of less than 30 nm, such as less than or equal to 26 nm. This can optionally be the case for any embodiment of the present disclosure that involves the silica aerogel sheet. The average pore size can be determined using a Quantachrome “autosorb-iQ” gas absorption analyzer, which is commercially available from Anton Paar (Graz, Austria) along with calculating average pore size using density functional theory (DFT) calculations.
Further, the silica aerogel sheet can also have a specific surface area of at least 800 m2/g, such as greater than or equal to 850 m2/g or perhaps greater than or equal to 900 m2/g. This can optionally be the case for any embodiment of the present disclosure that involves the silica aerogel sheet, preferably in combination with an average pore diameter in one or both ranges noted in the paragraph above and/or in combination with a density of between 100 mg/cc and 150 mg/cc, optionally in further combination with visible transmission and haze levels in the ranges noted above (e.g., Tvis greater than 98% together with haze of less than 2.5%, less than 2%, or less than 1.75%). The specific surface area can also be determined using a Quantachrome “autosorb-iQ” gas absorption analyzer, which is commercially available from Anton Paar (Graz, Austria) along with calculating specific surface area using density functional theory (DFT) calculations.
The silica aerogel sheet can also have a linear shrinkage (X/Y direction) of less than 3%, such as less than 2.7%, less than 2.5%, less than 2% or perhaps less than 1.75%. Linear shrinkage can be determined by taking an image of a silica wet gel sample before drying and an image of the silica aerogel sample after drying. The images can be taken with a regular camera with a known scale. The images can be analyzed with image J software and the final length of the silica aerogel can be determined with respect to the known initial length before drying.
The silica aerogel sheet can also have less than 3% solvent remaining after drying, such as less than 2.5%, less than 2% or less that 1.75%. The % solvent remaining can be determined by using an analytical balance to obtain a mass of the sample. An initial mass of the sample is first obtained in a room temperature environment after CPD drying. The sample is placed in a ceramic oven at 150° C. and heat treated for a minimum of 2 hours to evaporate solvent molecules. A final mass of the sample is obtained after heat treatment and the % solvent remaining is calculated using the following equation:
Solvent Remaining (SR), wt %={(Mo−Mf)/Mo}*100
where,
The silica aerogel sample can also have a maximum strain at complete breaking point of at least 2.5%, such as at least 3%, at least 3.1% or perhaps at least 3.2%. Maximum strain % at complete breaking point is the highest deformation value obtained from the x-axis of a stress-strain (s-s) curve for an aerogel sample. Again, the flexural stress-strain (s-s) curve is produced by a flexural test performed in accordance with ASTM D790: Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Material, the contents of which are incorporated herein by reference. Further, the silica aerogel sample can have a maximum resilience at complete breaking point of greater than 400 J/m3, such as 425 J/m3. Maximum resilience is determined by calculating a maximum area under the flexural stress-strain (s-s) curve for the aerogel sample.
Exemplary silica aerogel sheets were prepared as outlined below. Additionally, comparative exemplary silica aerogel sheets were attempted. Properties for silica aerogel sheets obtained were also measured using methods described herein and tabulated in Tables 1-3.
Example #1 was prepared according to the following steps:
Example #2 was prepared according to the following steps:
Example #3 was prepared according to the following steps:
In Example #4, ten silica aerogel sheet samples were prepared according to steps of Example #3. Properties obtained for the resulting silica aerogel sheets are shown in Table 3. Further, haze versus shrinkage properties are shown in
Comparative Example #1 was prepared according to the following steps:
Comparative Example #2 was prepared according to the following steps:
Comparative Example #3 was prepared according to the following steps:
Comparative Example #4 was prepared according to the following steps:
Comparative Example #5 was prepared according to the following steps:
In Comparative Example #6, four silica aerogel sheet samples were prepared according to steps A through G and I of Example #4. However, step H was performed using an ethanol solvent bath instead of a methanol solvent bath. Properties obtained for the resulting silica aerogel sheets are shown in Table 3 and
In Comparative Example #7, twelve samples of silica wet gels were prepared according to steps A through G and I of Example #4. However, step H was performed using an IPA solvent bath instead of a methanol solvent bath. Properties obtained for the resulting silica aerogel sheets are shown in Table 3 and
As shown in Table 1, optimal results were obtained with the recipe of Example 1 when using a precursor material having methyl silicate 51 as the silicon alkoxide. When TMOS, MTMS and TEOS were used, silica wet gels were not obtained.
As shown in Table 2, optimal results are obtained with a precursor material having a weight percent ratio of the methyl silicate 51:water in the range of between 0.25:1 and 2:1. Examples 1-3 show that precursor materials having a ratio within this range yield a silica aerogel having a visible transmission of greater than or equal to 98% and a haze of less than or equal to 1.5%. Comparative Example 4 shows that a precursor material having a ratio above this range had a much lower visible transmission and higher haze. Comparative Example 5 shows that precursor material having a ratio below this range did not even form a wet gel.
As shown in Table 3 and
Finally,
Thus, one group of embodiments involves a precursor material having a weight percent ratio of the methyl silicate 51:water in the range of between 0.25:1 and 2:1, and where the resulting silica aerogel sheet having a visible transmission of greater than or equal to 98% and a haze of less than or equal to 1.5%. This can optionally be in combination with the resulting silica aerogel sheet having a density in a range of from about 100 mg/cc to about 200 mg/cc.
Some embodiments provide an article 10.
The silica aerogel sheet 300 preferably is adhered to a surface 14 of the glass sheet 12. By saying the aerogel sheet 300 is “adhered to” a surface of a glass sheet, this does not require a separate adhesive, though an adhesive can optionally be used. It also does not require the aerogel to contact the glass; there may be a coating or layer therebetween. Thus, although “adhered to” may involve direct contact, the broader meaning as used herein is “carried alongside.” This can optionally mean the aerogel is supported by the glass surface, and in some preferred embodiments the aerogel does contact the glass surface. In some embodiments, there is at most one layer (e.g., an optical adhesive layer) between the aerogel sheet 300 and the glass sheet 12.
A variety of known glass types can be used for the glass sheet 12, including soda-lime glass, borosilicate glass or aluminosilicate glass. In some cases, it may be desirable to use “white glass,” a low iron glass, etc. For some applications, it may be desirable to use tinted glass for the glass sheet 12. Moreover, there may be applications where the glass sheet 12 is formed of extremely thin, flexible glass, such as glass sold under the trademark Willow glass by Corning Inc. (Corning, New York, U.S.A.). If desired, the glass sheet 12 may be formed of a chemically strengthened glass, such as glass sold under the trademark Gorilla glass by Corning Inc. In certain embodiments, the glass sheet is part of a window, door, skylight, or other glazing. In alternative embodiments, the glass sheet 12 is replaced with a sheet formed of a polymer, such as polycarbonate, acrylic, or PVC. Various other polymer materials (e.g., transparent polymers) may be used in such alternative embodiments.
Glass sheets of various sizes can be used. Commonly, large-area glass sheets are used. For example, the glass sheet 12 can have a major dimension (e.g., a length or width) of at least about 0.1 meter, preferably at least about 0.5 meter, more preferably at least about 1 meter, perhaps more preferably at least about 1.5 meters (e.g., between about 2 meters and about 4 meters), and in some cases at least about 3 meters. In some embodiments, the glass sheet 12 is a jumbo glass sheet having a length and/or width that is between about 3 meters and about 10 meters, e.g., a glass sheet 12 having a width of about 3.5 meters and a length of about 6.5 meters.
Glass sheets of various thicknesses can be used. In some embodiments, the glass sheet 12 can have a thickness of about 1-8 mm. In some cases, the glass sheet 12 has a thickness of between about 2.3 mm and about 4.8 mm, and perhaps more preferably between about 2.5 mm and about 4.8 mm. In one particular embodiment, the glass sheet 12 has a thickness of about 3 mm.
Other embodiments provide a method of making an article.
In some embodiments, the step 245 comprises placing the silica aerogel sheet in contact with the glass sheet, and the silica aerogel sheet adheres to the glass sheet through van der Waals forces. In other embodiments, the step 245 comprises adhering the silica aerogel sheet to a glass sheet by an optical adhesive, optionally such that portions of the silica aerogel sheet are devoid of the optical adhesive. In embodiments of this nature, the optical adhesive can optionally be located only at a perimeter of the silica aerogel sheet.
Thus, the aerogel fabrication method can include various techniques, such as method 200D shown in
Some embodiments provide an insulating glazing unit.
In some cases, the silica aerogel sheet 300 is a single aerogel sheet. In such cases, there is only one silica aerogel sheet 300 in the between-pane space 50. The single aerogel sheet 300 can, for example, have a major dimension (e.g., a length or width) of at least 0.375 meter, preferably at least about 0.75 meter, or in some cases at least about 1.125 meters (e.g., between about 1.5 meters and about 3 meters).
In other cases, the silica aerogel sheet 300 comprises plurality of silica aerogel sheets. In such cases, there are a plurality of silica aerogel sheets in the between-pane space 50. A plurality of aerogel sheets may thus collectively define the silica aerogel sheet 300. When multiple aerogel sheets are used, they can be arranged in a tiled configuration between the two glass panes 100, 110. When a tiled configuration is used, multiple aerogel sheets preferably are arranged in a non-overlapping manner so as to cover a majority (i.e., greater than 50%, preferably at least 75%) of the area of an adjacent interior glass surface 120, 130.
Whether the silica aerogel sheet 300 is formed by one or multiple aerogel sheets, it preferably covers more than 60% (e.g., more than 70%, more than 80%, or even more than 90%) of an adjacent interior glass surface 120, 130. A coverage within any one or more (e.g., all) of these ranges can optionally be used in any embodiment of the present disclosure. In preferred embodiments, the silica aerogel sheet 300 consists of a single aerogel sheet. This can optionally be the case for any embodiment of the present disclosure involving a silica aerogel sheet.
When the silica aerogel sheet 300 comprises a plurality of aerogel sheets, those sheets can have any desired shape and tiling arrangement. As non-limiting examples, the aerogel sheets can be square, rectangular, or hexagonal in shape. In some embodiments, edges of each aerogel sheet are aligned both vertically and horizontally with edges of adjacent aerogel sheets. Reference is made to U.S. patent application Ser. No. 17/390,178, the teachings of which relating to aerogel sheet tiling arrangements are hereby incorporated by reference.
When multiple silica aerogel sheets are provided in a tiling arrangement, the size of the silica aerogel sheets is not particularly limited. In some cases, all of the silica aerogel sheets have the same dimensions. In other cases, some of the silica aerogel sheets have different dimensions (e.g., a greater length) compared to some of the other silica aerogel sheets. Preferably, each of the silica aerogel sheets has a length and a width of at least 10 cm. For each of the silica aerogel sheets, the length, the width, or both are preferably less than 1 meter. Such dimensions allow the silica aerogel sheets to be scaled-up so as to cover large areas between two glass sheets of an insulating glazing unit, while still allowing the silica aerogel sheets to be dried using a small high-pressure vessel. Larger or smaller silica aerogel sheets may alternatively be used.
In certain embodiments, the between-pane space 50 contains a gaseous atmosphere, preferably comprising a thermally insulative gas, such as argon, krypton, or both. In some cases, the gaseous atmosphere comprises a mix of argon and air (e.g., 90% argon and 10% air). In other cases, the gaseous atmosphere comprises a mix of krypton and air. In still other cases, the gaseous atmosphere comprises a mix of argon, krypton, and air. In yet other cases, the gaseous atmosphere is just air.
In certain cases, a gas gap G is provided in the between-pane space 50 alongside the silica aerogel sheet 300. In some cases, the gas gap G can have a width in a range of from 9 to 14 mm and it contains a gaseous atmosphere comprising argon, air, or both. In certain cases, between-pane space has a width W in a range of from 14 to 21 mm, the gaseous atmosphere comprises argon, and the width of the gas gap G is from 10.5 to 13.5 mm. Reference is made to U.S. patent application Ser. No. 17/389,603, the teachings of which relating to gas gap and between-pane space configurations are hereby incorporated by reference.
Certain embodiments include a spacer 60 between the two glass sheets 100, 110. The spacer 60 may be a conventional metal channel spacer, e.g., formed of stainless steel or aluminum. Or it can comprise polymer and metal, or just polymer (e.g., foam). The spacer can alternatively be an integral part of a sash, frame, etc. so as to maintain the IG unit in the desired configuration.
The spacer 60 can be adhered to the two glass sheets 100, 110 by one or more beads of sealant as is conventional and well-known to skilled artisans. In
In some embodiments, the silica aerogel sheet 300 does not contact the spacer 60. For example, the aerogel sheet 300 may be separated (i.e., spaced-apart) from the spacer 60 by about 1 mm to about 5 mm (e.g., about 2-4 mm, such as about 3 mm). When provided, the sealant 55, 58 between the spacer 60 and the two adjacent glass sheets 100, 110 can also be spaced from the silica aerogel sheet 300.
The first glass sheet 100 has opposed surfaces 120, 125, which preferably are opposed major surfaces (or “opposed faces”). Similarly, the second glass sheet 110 has opposed surfaces 130, 135, which preferably are opposed major surfaces. In some cases, surfaces 120 and 130 are interior surfaces facing a between-pane space 50, while surfaces 125 and 135 are exterior surfaces, e.g., such that surface 135 is an exterior surface exposed to an outdoor environment (and thus exposed to periodic contact with rain). This, however, is not required.
In some embodiments, the second glass sheet 110 is an outboard pane that defines both a #1 surface (i.e., surface 135) and a #2 surface (i.e., surface 130), while the first glass sheet 100 is an inboard pane that defines both a #3 surface (i.e., surface 120) and a #4 surface (i.e., surface 125). The IG unit 40 can optionally be mounted in a frame such that the #1 surface is exposed to an outdoor environment, while the #4 surface is exposed to an indoor environment (e.g., an environment inside a building).
The silica aerogel sheet 300 can be adhered to or otherwise mounted alongside either the #2 surface or the #3 surface of the insulating glazing unit 40. Another option is to have aerogel sheets on both the #2 and the #3 surfaces.
While
The silica aerogel sheet 300 has a thickness T. In some embodiments, the silica aerogel sheet 300 has a thickness in a range of from 1.5 mm to 15 mm, such as greater than 2 mm but less than 8 mm, or from 2 mm to 4 mm (e.g., 3 mm). It is to be appreciated, however, that other thicknesses can be used.
The between-pane space 50 has a thickness W, which is measured from the interior surface 130 of the second glass pane 110 to the interior surface 120 of the first glass pane 100. In certain embodiments, the silica aerogel sheet 300 does not occupy the entire thickness W of the between-pane space 50. In other cases, the silica aerogel sheet occupies the entire thickness of the between-pane space.
A ratio of the thickness T of the silica aerogel sheet 300 to the thickness W of the between-pane space 50 preferably is between 0.15 and 0.85. In some embodiments, the thickness
W of the between-pane space 50 is at least 10 mm, optionally together with the thickness of the silica aerogel sheets 300 being greater than 2 mm but less than 8 mm. In certain preferred embodiments, the aerogel sheet 300 occupies less than 50% of the thickness W of the between-pane space 50 (e.g., less than 45%, less than 40%, or even less than 35% of the thickness W of the between-pane space 50).
In other embodiments, the silica aerogel sheet 300 occupies a majority of the thickness W of the between-pane space 50. In such instances, the thickness T of the silica aerogel sheet 300 preferably is greater than 8 mm but less than 15 mm (e.g., about 10 mm), while the thickness of the gas gap G alongside the silica aerogel sheet 300 is optionally less than 5 mm (e.g., about 3 mm).
Certain embodiments provide an insulating glazing unit 40 that includes both a silica aerogel sheet 300 and a low-emissivity coating 70. In some cases, the silica aerogel sheet 300 is provided on an interior surface of one glass sheet and the low-emissivity coating 70 is provided on an interior surface of the other glass sheet.
When provided, the optional low-emissivity coating 70 preferably includes at least one silver-inclusive film, which desirably contains more than 50% silver by weight (e.g., a metallic silver film). In certain preferred embodiments, the low-emissivity coating 70 includes three or more infrared-reflective films (e.g., silver-containing films). Low-emissivity coatings having three or more infrared-reflective films are described in U.S. application and patent No. 11/546,152 and U.S. Pat. Nos. 7,572,511 and 7,572,510 and 7,572,509 and Ser. No. 11/545,211 and U.S. Pat. Nos. 7,342,716 and 7,339,728, the teachings of each of which are incorporated herein by reference. In some cases, the low-emissivity coating 70 includes four silver layers. In other cases, the low-emissivity coating can be a “single silver” or “double silver” low-emissivity coating, which are well-known to skilled artisans. Advantageous coatings of this nature are commercially available from, for example, Cardinal CG Company (Eden Prairie, Minnesota, U.S.A.).
Certain embodiments provide an insulating glazing unit 40 that includes both a silica aerogel sheet 300 and an optional transparent conductive oxide coating 85. In some cases, the silica aerogel sheet 300 is provided on an interior surface of a glass sheet and a transparent conductive oxide coating 85 is provided on an exterior surface of a glass sheet.
When provided, the optional transparent conductive oxide coating 85 can include indium tin oxide. In alternate embodiments, zinc aluminum oxide, SnO:Sb, sputtered SnO:F, or another known transparent conductive oxide is used. In some cases, transparent conductive oxide coating comprises tin oxide together with antimony, fluorine, or another dopant. Further, in some cases, the transparent conductive oxide coating 85 is a sputtered film. In other embodiments, the transparent conductive oxide coating 85 comprises a pyrolytic film that includes tin (e.g., comprising tin oxide together with antimony, fluorine, or another dopant). Also, in some cases, the transparent conductive oxide coating 85 includes carbon nanotubes.
Preferably, the transparent conductive oxide coating 85 is provided at a thickness of 10,000 Å or less, such as between about 1,000 Å and about 7,000 Å, e.g., from 1,000 Å to 1,750 Å, such as about 1,300-1,600 Å. For any embodiment where the transparent conductive oxide coating 85 is provided, it can optionally comprise a transparent conductive oxide film having a thickness of from 1,000 Å to 1,750 Å.
The transparent conductive oxide coating 85 can, for example, be a coating of the type described in any of U.S. Pat. Nos. 9,862,640 or 10,000,965 or or Ser. No. 16/740,006, the teachings of which concerning the transparent conductive oxide coating are hereby incorporated herein by reference. In the embodiment of
In some cases, the insulating glazing unit 40 includes both a transparent conductive oxide coating 85 and a low-emissivity coating 70. This, however, is not required in all embodiments. For example, in some cases, the insulating glazing unit 40 includes the low-emissivity coating 70 but is devoid of the transparent conductive oxide coating 85.
Other embodiments provide a method of making an insulating glazing unit. The method can include either method 200D shown in
In cases where method 200D is used, the step of assembling the silica aerogel sheet as part of an insulating glazing unit can include a step of adhering the silica aerogel sheet to a surface of a glass sheet (e.g., through van der Waals forces, or by using an optical adhesive). The silica aerogel sheet may be placed either manually or, more preferably, with robotics. In some embodiments, the silica aerogel sheet is adhered to a temporary surface for handling and placement. The silica aerogel sheet can be picked up using electrostatic adhesion, e.g., using commercially available Stackit robots manufactured by Grabit, Inc. (Sunnyvale, California, U.S.A.) or using technology described in U.S. Patent Application No. 63/387,442, the contents of which are incorporated herein by reference.
Certain embodiments provide a laminated glass assembly.
The silica aerogel sheet 300 can have any of the features and properties discussed elsewhere herein Likewise, the silica aerogel sheet 300 of the laminated glass assembly 80 can have the same dimensions and material properties as the silica aerogel sheet 300 described elsewhere herein for the insulating glazing unit 40.
The laminated glass assembly 80 can also include a polymer interlayer 400. The polymer interlayer 400 preferably is a tear-resistant polymer layer. In some cases, it is a sheet of ionoplast plastic. In other cases, it is a sheet of polyvinyl butyral (PVB). Various other materials known to be suitable for the interlayer of a laminated glass panel can also be used. In certain embodiments, both glass sheets 100, 110 can be clear 3 mm soda-lime float glass and the polymer interlayer 400 can be 0.30-inch thick PVB. It is to be appreciated, however, that these details are by no means limiting.
Other embodiments provide a method of making a laminated glass assembly. Here too, the method can include either method 200D shown in
In cases where method 200D is used, the step of assembling the silica aerogel sheet as part of a laminated glass assembly can include a step of adhering the silica aerogel sheet to a surface of a glass sheet (e.g., through van der Waals forces, or by using an optical adhesive) as described elsewhere herein. The silica aerogel sheet and glass sheet can then be assembled as part of a laminated glass assembly, using any suitable techniques. In some cases, the assembly process includes one or more steps described in U.S. Pat. Nos. 7,117,914 and 7,143,800, the teachings of which are hereby incorporated herein by reference.
While some preferred embodiments of the invention have been described, it should be understood that various changes, adaptations and modifications may be made therein without departing from the spirit of the invention and the scope of the appended claims.
This application is a continuation-in-part of U.S. patent application Ser. No. 18/181,342, filed Mar. 9, 2023, which in turn claims priority to U.S. patent application No. 63/318,165, filed Mar. 9, 2022, the contents of each of which are hereby incorporated by reference. This application is also related to U.S. patent application Ser. Nos. 18/181,357 and 18/181,368, each also filed Mar. 9, 2023 and the contents of each of which are hereby incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| 63318165 | Mar 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 18181342 | Mar 2023 | US |
| Child | 18462927 | US |
