In some electronic devices, physical security mechanisms may be used to protect sensitive hardware and/or software (e.g., cryptographic modules). An example of a physical security standard is the United States Government Federal Information Processing Standards (FIPS) 140-2 Security Requirements for Cryptographic Modules—Level 4. The standard states that “[a]t this security level, the physical security mechanisms provide a complete envelope of protection around the cryptographic module with the intent of detecting and responding to all unauthorized attempts at physical access” (FIPS 140-42).
According to an embodiment, a secured device is disclosed that includes an electronic component and a protective cover surrounding the electronic component. The secured device also includes one or more chemiluminescent reactant layers and a light sensor that is electrically connected to the electronic component. The one or more chemiluminescent reactant layers are disposed between the protective cover and the electronic component and include multiple reactants that undergo a chemiluminescent reaction. The light sensor is configured to trigger one or more tamper response operations responsive to detection of a photon generated by the chemiluminescent reaction.
According to another embodiment, a process of utilizing chemiluminescence for tamper event detection is disclosed. The process includes detecting, by a light sensor, a photon generated by a chemiluminescent reaction. The light sensor is electrically connected to an electronic component of a secured device that includes a protective cover surrounding the electronic component. A compressive force associated with a physical access attempt results in the chemiluminescent reaction within one or more chemiluminescent reactant layers disposed between the protective cover and the electronic component. The process also includes triggering one or more tamper response operations responsive to detecting the photon generated by the chemiluminescent reaction.
According to another embodiment, an electronic device is disclosed that includes a printed circuit board that includes a light sensor disposed on a surface of the printed circuit board. An optically transparent layer overlies the surface of the printed circuit board, and one or more chemiluminescent reactant layers overly the optically transparent layer. The one or more chemiluminescent reactant layers include multiple reactants that undergo a chemiluminescent reaction. The electronic device also includes a protective cover that surrounds the one or more chemiluminescent reactant layers, the optically transparent layer, and the printed circuit board. The light sensor is configured to trigger one or more tamper response operations responsive to detection of a photon generated by the chemiluminescent reaction.
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts of exemplary embodiments of the invention.
Secured devices, such as encryption modules, that are resistant to physical tampering are used in various computing systems to protect sensitive data and components. For example, stored data that might be effectively invulnerable to unauthorized access via software protocols might be relatively easily accessed by direct, physical means, even if the stored data is notionally protected by encryption. Such physical access might entail drilling through, or physical removal of, portions of an outer casing or packaging of an electronic component. Physical access to internal device components might allow various data protective features of the device to be overridden or avoided such that otherwise protected data could be accessed. For example, by making direct electrical connections to various internal components, an encryption module might be effectively disabled or overridden. Alternatively, physical access to internal device components might allow incoming and outgoing data to be monitored or redirected in an unauthorized manner. Furthermore, in some instances, even physical access to internal components merely for purposes of studying a device might be harmful from the standpoint of security in similar installed devices.
The present disclosure describes utilizing chemiluminescence for tamper event detection in a secured device that is designed to be resistant to physical tampering in order to protect sensitive data and/or components of the secured device. Chemiluminescence is the emission of photons as the result of a chemical reaction. In the present disclosure, the secured device may include one or more chemiluminescent reactant layers that include reactants that undergo a chemiluminescent reaction when mixed. An attempt to physically access the secured device may cause the reactants to mix, resulting in the chemiluminescent reaction. The secured device may include one or more light sensors configured to detect photons generated within the chemiluminescent reactant layer(s) as a result of the chemiluminescent reaction. The light sensor(s) may be configured to trigger one or more tamper response operations (e.g., erasing data, disabling component(s), etc.).
In a particular embodiment, the secured device may include multiple chemiluminescent reactant layers and a fracturable barrier layer (e.g., glass) positioned between the individual chemiluminescent reactant layers. In this case, an attempt to physically access the secured device may result in application of a compressive force that fractures the barrier layer, enabling a first reactant (or a first set of multiple reactants) in a first chemiluminescent reactant layer to mix with a second reactant (or a second set of multiple reactants) in a second chemiluminescent reactant layer, resulting in the chemiluminescent reaction. In another embodiment, the secured device may include light generating microcapsules dispersed within a chemiluminescent reactant layer. The microcapsules include multiple compartments to isolate the first reactant(s) from the second reactant(s) within the same microcapsule, such as shell-in-shell microcapsules. In this case, an attempt to physically access the secured device may result in application of a compressive force to the microcapsule. The compressive force may result in rupture of an inner shell, enabling the first reactant(s) and the second reactant(s) to mix and undergo a chemiluminescent reaction within the microcapsule. An outer shell of the microcapsule may be formed from a material that enables a substantial portion of the light generated within the microcapsule to exit the microcapsule for detection by the light sensor(s) of the secured device.
As used herein, the term “light” is used to refer to ultraviolet (UV) light (in a wavelength range of 10 nm to 400 nm), visible light (e.g., in a wavelength range of 400 nm to 700 nm), or infrared light (e.g., above 700 nm) that may be produced as a result of a chemiluminescent reaction. As used herein, the term “microcapsule” is used to refer to capsules that are in a range of about 10 microns to 1000 microns in diameter. However, it will be appreciated that the following disclosure may be applied to capsules having a smaller size (also referred to as “nanocapsules”).
In some cases, the chemiluminescent reactant layer(s) 150 may include a fracturable barrier layer (e.g. glass) positioned between a first chemiluminescent reactant layer and a second chemiluminescent reactant layer, as illustrated and further described herein with respect to
The optically transparent layer 140 may be sufficiently transparent to photons of a particular wavelength within a photon emission distribution spectrum associated with a particular chemiluminescent reaction to enable at least a portion of the photons generated within the chemiluminescent reactant layer(s) 150 to reach the light sensor(s) 130. While not shown in the example of
The light sensor(s) 130 may enable passive detection of a physical access attempt. In some cases, the secured device 100 may include or may be electrically connected to a battery (not shown in
In a particular embodiment, the tamper response operation(s) may correspond to one or more actions to prevent or limit access to a component (e.g., the internal component 110) of the secured device 100. To illustrate, the action(s) may include shutting down the internal component 110 or a portion thereof, transmitting an alarm signal to the internal component 110, transmitting an alarm signal to an external component, sounding an audible alarm, triggering a visual alarm, rendering the internal component 110 inoperable, physically destroying the internal component 110 or a portion thereof, erasing electronically stored data, encrypting internal data, overwriting stored data with dummy data, or any combination thereof (among other alternatives).
Thus,
Referring to
The chemiluminescent reaction depicted in
It will be appreciated that a variety of dyes may be selected for incorporation into the chemiluminescent reactant layer(s) 150. A particular dye may emit photons having a particular wavelength within a photon emission distribution spectrum associated with the particular dye. The light sensor(s) 130 may be configured to detect photons having wavelengths within a photon emission distribution spectrum associated with a selected dye. As an illustrative, non-limiting example, 9,10-diphenylanthracene is a dye that has a photon emission distribution spectrum with a marked emission peak at 405 nm and appreciable emission at 436 nm. In this case, the light sensor(s) 130 may be configured to detect photons within the photon emission distribution spectrum associated with 9,10-diphenylanthracene.
In a particular embodiment, the chemiluminescent reaction may correspond to the chemiluminescent reaction of
Responsive to detection of photons generated within the chemiluminescent reactant layer(s) 150, the light sensor(s) 130 may be configured to trigger one or more tamper response operations. In a particular embodiment, the tamper response operation(s) may correspond to one or more actions to prevent or limit access to a component (e.g., the internal component 110) of the secured device 300. To illustrate, the action(s) may include shutting down the internal component 110 or a portion thereof, transmitting an alarm signal to the internal component 110, transmitting an alarm signal to an external component, sounding an audible alarm, triggering a visual alarm, rendering the internal component 110 inoperable, physically destroying the internal component 110 or a portion thereof, erasing electronically stored data, encrypting internal data, overwriting stored data with dummy data, or any combination thereof (among other alternatives).
Thus,
In a particular embodiment, the chemiluminescent reaction may correspond to the chemiluminescent reaction of
In the particular embodiment depicted in
As illustrated and further described herein with respect to
As described further herein, the chemiluminescent reaction generates photons within a particular wavelength range that is detectable by the light sensor(s) 130 of the secured device 400. The outer wall 422 of the microcapsule 420 allows a substantial portion of the photons generated within the microcapsule 420 as a result of the chemiluminescent reaction to pass through the outer wall 422 into the surrounding matrix material 406 and into the adjacent optically transparent layer 140. The outer wall 422 can be made from chemically non-reactive materials, such as some plastics which are transparent, translucent, or light filtering to pass the curing wavelengths of light from chemiluminescent light source into the interface material 406. In an embodiment, the outer wall 422 has a transmittance value of at least 90% for the particular emitted photon wavelength(s). In certain embodiments, the outer wall 422 may include a natural polymeric material, such as gelatin, arabic gum, shellac, lac, starch, dextrin, wax, rosin, sodium alginate, zein, and the like; semi-synthetic polymer material, such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl ethyl cellulose; full-synthetic polymer material, such as polyolefins, polystyrenes, polyethers, polyureas, polyethylene glycol, polyamide, polyurethane, polyacrylate, epoxy resins, among others.
Thus,
In
Thus,
In each of the stages 5(a)-5(f), the structure is shown in a cross-sectional side view. Referring to
In the example depicted in
An example of a technique of preparing magnetite nanoparticles follows. A 5 mol/l NaOH solution is added into a mixed solution of 0.25 mol/l ferrous chloride and 0.5 mol/l ferric chloride (molar ratio 1:2) until obtaining pH 11 at room temperature. The slurry is washed repeatedly with distilled water. Then, the resulting magnetite nanoparticles are magnetically separated from the supernatant and redispersed in aqueous solution at least three times, until obtaining pH 7. A typical average diameter of the resulting magnetite nanoparticles may be about 12 nm.
The microparticle system described with respect to
In this example, the fabrication of polyelectrolyte capsules is based on the layer-by-layer (LbL) self-assembly of polyelectrolyte thin films. Such polyelectrolyte capsules are fabricated by the consecutive adsorption of alternating layer of positively and negatively charged polyelectrolytes onto sacrificial colloidal templates. Calcium carbonate is but one example of a sacrificial colloidal template. One skilled in the art will appreciate that other templates may be used in lieu of, or in addition to, calcium carbonate.
The method 500 continues by LbL coating the CaCO3 microparticles (operation 504). In operation 504, a polyelectrolyte multilayer (PEM) build-up may be employed by adsorbing five bilayers of negative PSS (poly(sodium 4-styrenesulfonate); Mw=70 kDa) and positive PAH (poly(allylamine hydrochloride); Mw=70 kDa) (2 mg/mL in 0.5 M NaCl) by using the layer-by-layer assembly protocol. For example, the CaCO3 microparticles produced in operation 502 may be dispersed in a 0.5 M NaCl solution with 2 mg/mL PSS (i.e., polyanion) and shaken continuously for 10 min. The excess polyanion may be removed by centrifugation and washing with deionized water. Then, 1 mL of 0.5 M NaCl solution containing 2 mg/mL PAH (i.e., polycation) may be added and shaken continuously for 10 min. The excess polycation may be removed by centrifugation and washing with deionized water. This deposition process of oppositely charged polyelectrolyte may be repeated five times and, consequently, five PSS/PAH bilayers are deposited on the surface of the CaCO3 microparticles. One of the resulting polymer coated CaCO3 microparticles is shown at stage 5(c).
The thickness of this “inner shell” polyelectrolyte multilayer may be varied by changing the number of bilayers. In some cases, it may be desirable for the inner shell to rupture while the outer shell remains intact. Typically, for a given shell diameter, thinner shells rupture more readily than thicker shells. Hence, in accordance with some embodiments of the present disclosure, the inner shell is made relatively thin compared to the outer shell. On the other hand, the inner shell must not be so thin as to rupture prematurely.
The PSS/PAH-multilayer in operation 504 is but one example of a polyelectrolyte multilayer. One skilled in the art will appreciate that other polyelectrolyte multilayers and other coatings may be used in lieu of, or in addition to, the PSS/PAH-multilayer in operation 504.
The method 500 continues by preparing ball-in-ball calcium carbonate microparticles in which Second Reactant(s) (which can be any suitable oxidant, including hydrogen peroxide) is immobilized by a second coprecipitation (operation 506). “Immobilize” means “removing from general circulation, for example by enclosing in a capsule.” The ball-in-ball CaCO3 microparticles are characterized by a polyelectrolyte multilayer that is sandwiched between two calcium carbonate compartments. In operation 506, the polymer coated CaCO3 microparticles may be resuspended in 1M CaCl2 (0.615 mL), 1M Na2CO3 (0.615 mL), and deionized water (2.500 mL) containing hydrogen peroxide (1 mg), rapidly mixed and thoroughly agitated on a magnetic stirrer for about 20 seconds at about room temperature. After the agitation, the precipitate may be separated from the supernatant by centrifugation and washed three times with water. The second coprecipitation is accompanied by formation of a coproduct, i.e., single core CaCO3 microparticles that contain only hydrogen peroxide. The ball-in-ball CaCO3 microparticles, which are magnetic due to the immobilized magnetite nanoparticles in the inner compartment, may be isolated by applying an external magnetic field to the sample while all of the nonmagnetic single core CaCO3 microparticles are removed by a few washing steps. One of the resulting ball-in-ball CaCO3 microparticles is shown at stage 5(d).
In an embodiment, the outer shell wall material is made of a material for the chemiluminescent photon to escape the shell. In another embodiment, the outer shell wall material is made of a material where the photon yield outside the wall of the outer shell wall is maximized. In an embodiment, the outer shell wall has a transmittance of at least 90%. In certain embodiments, the outer shell wall material may include natural polymeric material, such as gelatin, arabic gum, shellac, lac, starch, dextrin, wax, rosin, sodium alginate, zein, and the like; semi-synthetic polymer material, such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl ethyl cellulose; full-synthetic polymer material, such as polyolefins, polystyrenes, polyethers, polyureas, polyethylene glycol, polyamide, polyurethane, polyacrylate, epoxy resins, among others. In certain embodiments, the method for wrapping a core material includes chemical methods such as interfacial polymerization, in situ polymerization, molecular encapsulation, radiation encapsulation; physicochemical methods such as aqueous phase separation, oil phase separation, capsule-heart exchange, pressing, piercing, powder bed method; and physical methods, such as spray drying, spray freezing, air suspension, vacuum evaporation deposition, complex coacervation, long and short centrifugation.
An example of a conventional preparation technique for the outer shell follows, and can be accomplished at stage 5(e). A gelatin is dissolved into n-hexane in a water bath at about 50° C. to obtain a 6% gelatin solution. The gelatin may optionally be swelled with deionized water before the preparation of the gelatin solution. The ball-in-ball CaCO3 microparticles prepared in operation 506 are added to the gelatin solution while stirring to form an emulsified dispersion system. The pH is then adjusted to about 3.5-3.8 using acetic acid, and then a 20% sodium sulfate solution is slowly added into the dispersion system while maintaining a temperature of about 50° C. The temperature of the dispersion system is then lowered to a temperature of about 15° C. The result is a colloid of gelatin coated ball-in-ball CaCO3 microparticles.
Operation 510 is a CaCO3 extraction. In operation 510, the CaCO3 core of the ball-in-ball CaCO3 microparticles may be removed by complexation with ethylenediaminetetraacetic acid (EDTA) (0.2 M, pH 7.5) leading to formation of shell-in-shell microcapsules. For example, the gelatin coated ball-in-ball CaCO3 microparticles produced in operation 508 may be dispersed in 10 mL of the EDTA solution (0.2 M, pH 7.5) and shaken for about 4 h, followed by centrifugation and re-dispersion in fresh EDTA solution. This core-removing process may be repeated several times to completely remove the CaCO3 core. The size of the resulting shell-in-shell microcapsules ranges from about 8 μm to about 10 μm, and the inner core diameter ranges from about 3 μm to about 5 μm. One of the resulting shell-in-shell microcapsules is shown at stage 5(f). Depending on the application of use, the shell-in-shell microcapsule can have a range of about 0.5 μm to about 200 μm.
As noted above, the fabrication of polyelectrolyte capsules in the method 500 of
As noted above, one skilled in the art will understand that various chemiluminescent reactants and oxidants can be used. Moreover, the multi-compartment microcapsule can utilize various chemiluminescent reactions. The chemistry used in chemiluminescent reactions is a mature technology, and those skilled in the art will know that additional materials can be further added to the multi-compartment microcapsule. For example, enhancing reagents such as alkyl dimethyl benzyl quaternary ammonium salt may be added to the reactants.
The photon-emitting reactants may be chosen to be inert with respect to the material of the microcapsule walls, or an isolating barrier within a microcapsule when the reactants are not in contact. The photon-emitting reactants also may be chosen to be inert with respect to the outer microcapsule wall when the reactants are in contact, or such that the chemical products of the reaction are inert with respect to the outer microcapsule wall, and any remnants of the inner microcapsule wall or barrier.
An amount of the first reactant and an amount of the second reactant may be determined. The amounts may be determined from the total amount of the reactants required to produce a desired amount of photons, the ratio of each reactant according to a reaction equation, the desired dimensions of the microcapsule, and the manner of isolating the reactants within the capsule. For example, a microcapsule may be desired having a maximum dimension less than or equal to a desired final thickness of less than 0.5 microns, and the amount of reactants may be chosen corresponding to the volume available within a microcapsule formed according to that dimension.
One or more inner microcapsules, such as illustrated by microcapsule 420 of
Further, an outer microcapsule may be formed containing the inner microcapsule(s) and one or more other reactants, in the manner of multi-compartment microcapsule 420 in
It will be understood from the foregoing description that modifications and changes may be made in various embodiments of the present invention without departing from its true spirit. The descriptions in this specification are for purposes of illustration only and are not to be construed in a limiting sense. The scope of the present invention is limited only by the language of the following claims.
Number | Name | Date | Kind |
---|---|---|---|
3481790 | Duddy | Dec 1969 | A |
3653372 | Douglas | Apr 1972 | A |
3656372 | Chana | Apr 1972 | A |
3689391 | Ullman | Sep 1972 | A |
4095583 | Petersen et al. | Jun 1978 | A |
4233402 | Maggio | Nov 1980 | A |
4273671 | Allinikov | Jun 1981 | A |
4278837 | Best et al. | Jul 1981 | A |
4598274 | Holmes | Jul 1986 | A |
4635166 | Cameron | Jan 1987 | A |
4772530 | Gottschalk et al. | Sep 1988 | A |
4811288 | Kleijne et al. | Mar 1989 | A |
4814949 | Elliott | Mar 1989 | A |
4816367 | Sakojiri et al. | Mar 1989 | A |
5169707 | Faykish et al. | Dec 1992 | A |
5319475 | Kay et al. | Jun 1994 | A |
5325721 | Pendergrass, Jr. | Jul 1994 | A |
5406630 | Piosenka | Apr 1995 | A |
5508893 | Nowak et al. | Apr 1996 | A |
5904795 | Murakami et al. | May 1999 | A |
5904796 | Freuler et al. | May 1999 | A |
5945995 | Higuchi et al. | Aug 1999 | A |
5984995 | White | Nov 1999 | A |
6114413 | Kang et al. | Sep 2000 | A |
6217213 | Curry et al. | Apr 2001 | B1 |
6235148 | Courson, Jr. | May 2001 | B1 |
6530527 | Ahlers et al. | Mar 2003 | B1 |
6758572 | Ladyjensky | Jul 2004 | B2 |
6776495 | Nomiyama | Aug 2004 | B2 |
6833191 | Bayless | Dec 2004 | B2 |
6876143 | Daniels | Apr 2005 | B2 |
6947285 | Chen et al. | Sep 2005 | B2 |
7005733 | Kommerling | Feb 2006 | B2 |
7065656 | Schwenck et al. | Jun 2006 | B2 |
7223964 | Wiese et al. | May 2007 | B2 |
7247791 | Kulpa | Jul 2007 | B2 |
7248359 | Boege | Jul 2007 | B2 |
7274791 | van Enk | Sep 2007 | B2 |
7290549 | Banerjee et al. | Nov 2007 | B2 |
7296299 | Schwenck et al. | Nov 2007 | B2 |
7362248 | McClure et al. | Apr 2008 | B2 |
7385491 | Doi | Jun 2008 | B2 |
7436316 | Fleischman | Oct 2008 | B2 |
7443176 | McClure et al. | Oct 2008 | B2 |
7488954 | Ross et al. | Feb 2009 | B2 |
7518507 | Dalzell | Apr 2009 | B2 |
7540621 | Goychrach | Jun 2009 | B2 |
7573301 | Walmsley | Aug 2009 | B2 |
7666813 | Hoefer et al. | Feb 2010 | B2 |
7806072 | Hamilton, II et al. | Oct 2010 | B2 |
7816785 | Iruvanti et al. | Oct 2010 | B2 |
7830021 | Wilcoxon et al. | Nov 2010 | B1 |
7834442 | Furman et al. | Nov 2010 | B2 |
7886813 | Hua et al. | Feb 2011 | B2 |
7889442 | Suzuki et al. | Feb 2011 | B2 |
7952478 | Bartley et al. | May 2011 | B2 |
8137597 | Brott | Mar 2012 | B1 |
8174112 | Karp et al. | May 2012 | B1 |
8198641 | Zachariasse | Jun 2012 | B2 |
8288857 | Das | Oct 2012 | B2 |
8310147 | Seo et al. | Nov 2012 | B2 |
8502396 | Buer et al. | Aug 2013 | B2 |
8522049 | Ahmadi | Aug 2013 | B1 |
8581209 | Oxley et al. | Nov 2013 | B2 |
8623418 | Liang et al. | Jan 2014 | B2 |
8647579 | La Grone | Feb 2014 | B2 |
8659908 | Adams et al. | Feb 2014 | B2 |
8741084 | Kisch et al. | Jun 2014 | B2 |
8741804 | Boday et al. | Jun 2014 | B2 |
8824040 | Buchheit et al. | Sep 2014 | B1 |
8865285 | Dagher et al. | Oct 2014 | B2 |
8896100 | Kishino et al. | Nov 2014 | B2 |
8896110 | Hu et al. | Nov 2014 | B2 |
9040252 | Della Ciana et al. | May 2015 | B2 |
9075018 | Geddes et al. | Jul 2015 | B2 |
9217736 | Ribi | Dec 2015 | B2 |
9245202 | Boday | Jan 2016 | B2 |
9263605 | Morgan | Feb 2016 | B1 |
9307692 | Boday | Apr 2016 | B2 |
9856404 | Campbell et al. | Jan 2018 | B2 |
9858780 | Campbell | Jan 2018 | B1 |
9896389 | Campbell | Feb 2018 | B2 |
10040993 | Brott | Aug 2018 | B1 |
10215648 | Pillars et al. | Feb 2019 | B1 |
10229292 | Campbell | Mar 2019 | B2 |
10318462 | Bartley | Jun 2019 | B2 |
10331911 | Kuczynski | Jun 2019 | B2 |
10357921 | Campbell | Jul 2019 | B2 |
10392452 | Campbell | Aug 2019 | B2 |
10508204 | Odarczenko | Dec 2019 | B2 |
10513735 | Swartz et al. | Dec 2019 | B2 |
10696761 | Campbell | Jun 2020 | B2 |
10696899 | Campbell | Jun 2020 | B2 |
20050068760 | Goychrach | Mar 2005 | A1 |
20060079021 | Yang | Apr 2006 | A1 |
20060228542 | Czubarow | Oct 2006 | A1 |
20070054762 | Tocco | Mar 2007 | A1 |
20070207284 | McClintic | Sep 2007 | A1 |
20080038540 | Hirayama et al. | Feb 2008 | A1 |
20080090942 | Hovorka | Apr 2008 | A1 |
20080277596 | Oxley | Nov 2008 | A1 |
20080286856 | Park et al. | Nov 2008 | A1 |
20090036568 | Merle et al. | Feb 2009 | A1 |
20090155571 | Mustonen | Jun 2009 | A1 |
20100006431 | Wallace et al. | Jan 2010 | A1 |
20120007249 | Kuo et al. | Jan 2012 | A1 |
20120077279 | Wiesner et al. | Mar 2012 | A1 |
20130034739 | Boday et al. | Feb 2013 | A1 |
20130179996 | Boday | Jul 2013 | A1 |
20140011049 | Stamm | Jan 2014 | A1 |
20140110049 | Yuen et al. | Apr 2014 | A1 |
20140368992 | Strader et al. | Dec 2014 | A1 |
20150038809 | Etzkorn | Feb 2015 | A1 |
20150166822 | Samsudin et al. | Jun 2015 | A1 |
20150246521 | Fathi et al. | Sep 2015 | A1 |
20150364710 | Chen et al. | Dec 2015 | A1 |
20160033497 | Wang et al. | Feb 2016 | A1 |
20160053169 | Kunath et al. | Feb 2016 | A1 |
20160067524 | Bourke, Jr. | Mar 2016 | A1 |
20160289484 | Lalgudi et al. | Oct 2016 | A1 |
20170015886 | Braun et al. | Jan 2017 | A1 |
20170027197 | Bourke, Jr. et al. | Feb 2017 | A1 |
20170029532 | Pandya | Feb 2017 | A1 |
20170129825 | Campbell et al. | May 2017 | A1 |
20170130102 | Campbell et al. | May 2017 | A1 |
20170130993 | Campbell et al. | May 2017 | A1 |
20170158886 | Odarczenko | Jun 2017 | A1 |
20170279532 | Bartley | Sep 2017 | A1 |
20180116060 | Campbell | Apr 2018 | A1 |
20180158305 | Noland et al. | Jun 2018 | A1 |
20180327659 | Campbell | Nov 2018 | A1 |
20180340032 | Campbell et al. | Nov 2018 | A1 |
20180371122 | Campbell et al. | Dec 2018 | A1 |
20180371123 | Campbell | Dec 2018 | A1 |
20190291357 | Campbell et al. | Sep 2019 | A1 |
20190309105 | Campbell et al. | Oct 2019 | A1 |
Number | Date | Country |
---|---|---|
918331 | Jan 1973 | CA |
103740978 | Apr 2014 | CN |
103740997 | Apr 2014 | CN |
2000317578 | Nov 2000 | JP |
2001176924 | Jun 2001 | JP |
4073571 | Feb 2008 | JP |
9733922 | Sep 1997 | WO |
WO-2009029804 | Mar 2009 | WO |
WO-2011086018 | Jul 2011 | WO |
WO-2013041871 | Mar 2013 | WO |
2014204828 | Dec 2014 | WO |
WO-2014204828 | Dec 2014 | WO |
WO-2016186336 | Nov 2016 | WO |
Entry |
---|
U.S. Appl. No. 15/603,686, to Eric J. Campbell et al., entitled, Light Generating Microcapsules for Self-Healing Polymer Applications, assigned to International Business Machines Corporation, 34 pages, filed May 24, 2017. |
U.S. Appl. No. 15/631,165, to Eric J. Campbell et al., entitled, Light Generating Microcapsules for Self-Healing Polymer Applications, assigned to International Business Machines Corporation, 33 pages, filed Jun. 23, 2017. |
U.S. Appl. No. 16/015,753, to Eric J. Campbell et al., entitled, Light Generating Microcapsules for Photo-Curing, assigned to International Business Machines Corporation, 33 pages, filed Jun. 22, 2018. |
Appendix P; List of IBM Patent or Applications Treated as Related, Oct. 16, 2018, 2 pages. |
Park et al., Smart Microplates: Integrated Photodiodes for Detecting Bead-Based Chemiluminescent Reactions, 5th IEEE Conference on Sensors, EXCO, (IEEE Sensors 2006), held Oct. 2006, Daegu, Korea, pp. 580-583, Institute of Electrical and Electronics Engineers (IEEE), DOI: 10.1109/ICSENS.2007.355534, USA. |
Zhan et al., Electrochemical Sensing in Microfluidic Systems Using Electrogenerated Chemiluminescence as a Photonic Reporter of Redox Reactions, JACS Articles, vol. 124, No. 44, Oct. 2002, pp. 13265-13270, American Chemical Society, Washington, D.C. |
Jorgensen et al., A Biochemical Microdevice With an Integrated Chemiluminescence Detector, Sensors and Actuators B: Chemical, vol. 90, Issue 1, Apr. 2003, pp. 15-21, Elsevier, Amsterdam, Netherlands. |
Previte et al., Microwave-Triggered Metal-Enhanced Chemiluminescence (MT-MEC): Application to Ultra-Fast and Ultra-Sensitive Clinical Assays, Journal of Fluorescence, vol. 16, Issue 5, Sep. 2006, pp. 641-647, Springer Science+Business Media, Berlin, Germany. |
Marzzacco, The Effect of a Change in the Catalyst on the Enthalpy of Decomposition of Hydrogen Peroxide, pp. 12-13, Chem 13 News, Nov. 2008, reprinted from pp. 16-17, May 2001, University of Waterloo, Waterloo, ON, Canada. |
Masin, The Chemistry of Hand Warmers, 3 pages, chemistryislife.com (online), accessed Jun. 5, 2017, URL: www.chemistryislife.com/the-chemistry-_of-hand-warmer. |
Unknown, Flameless Chemical Heaters, zenstoves.net (online), 4 pages, accessed Jun. 5, 2017, URL: http://zenstoves.net/Flameless.htm. |
Unknown, Flameless Ration Heater (FRH), MREInfo.com (online), 2014, 5 pages, accessed Jun. 5, 2017, URL: www.mreinfo.com/us/mre/frh.html. |
Kawashita et al., In vitro heat generation by ferrimagnetic maghemite microspheres for hyperthermic treatment of cancer under alternating magnetic field, Journal of Materials Science: Materials in Medicine, vol. 19, Issue 5, pp. 1897-1903, May 2008, (Abstract Only, 2 pages), URL: www.ncbi.nlm.nih.gov/pubmed/17914614. |
Unknown, PTFE Coatings, Specific Heat of Some Common Substances, engineeringtoolbox.com (online), 7 pages, accessed Jun. 5, 2017, URL: www.engineeringtoolbox.com/specific-heat-capacity-d_391.html. |
Unknown, Standard enthalpy change of formation (data table), Wikipedia.org (online), 13 pages, accessed Jun. 5, 2017, URL: en.wikipedia.org/wiki/Standard_enthalpy_change_of_formation_%28data_table%29. |
Unknown, Technical Overview: Microencapsulation, microteklabs.com (online), 4 pages, accessed Jun. 5, 2017, URL: www.microteklabs.com/technical_overview.pdf. |
Unknown, Thermochemistry, 7 pages, Olomouc—Hej{hacek over (c)}ín Gymnasium (online), 7 pages, accessed Jun. 5, 2017, URL: http://smd.gytool.cz/downloads/thermochemistry_bar.pdf. |
Delcea et al., Multicompartmental Micro- and Nanocapsules: Hierarchy and Applications in Biosciences, Macromolecular Bioscience, vol. 10, May 2010, pp. 465-474, Wiley-VCH Verlag GmbH & Co., Weinheim. |
Lee, Microencapsulated Heat Generating Material to Accelerate the Curing Process During Liquid Crystal Display Fabrication, NineSigma, Inc. (online), 2014 (month unknown), 3 pages, accessed Jun. 5, 2017, URL: https://ninesights.ninesigma.com/rfps/-/rfp-portlet/rfpViewer/2690. |
Brown et al., In situ poly(urea-formaldehyde) microencapsulation of dicyclopentadiene, Journal of Microencapsulation, Nov.-Dec. 2003, vol. 20, No. 6, pp. 719-730, Taylor & Francis Ltd (online, www.tandf.co.uk/journals), DOI: 10.1080/0265204031000154160. |
Keller et al., Mechanical Properties of Microcapsules Used in a Self-Healing Polymer, Experimental Mechanics, vol. 46, Nov. 2006, pp. 725-733, Society for Experimental Mechanics, Bethel, CT. |
Hu et al., Controlled Rupture of Magnetic Polyelectrolyte Microcapsules for Drug Delivery, Langmuir, vol. 24, Sep. 2008, pp. 11811-11818, American Chemical Society, USA. |
Unknown, Materials for Sealing Liquid Crystal, Three Bond Technical News, vol. 43, May 1994, pp. 1-8, Three Bond Europe, UK. |
Unknown, Advanced Technologies for LCD Assembly, DowCorning.com (online), 2014 (month unknown), 4 pages, accessed Jun. 5, 2017, URL: www.dowcorning.com/content/publishedlit/11-3437_Advanced_Technologies_LCD_Assembly.pdf?wt.svl=ELEC_LHH. |
Unknown, LOCTITE ECCOBOND DS 6601, Henkel.com (online), Mar. 2013, 2 pages, URL: https://tds.us.henkel.com/NA/UT/HNAUTTDS.nsf/web/C0DD8377AB27D63985257B41005DC4A1/$File/LOCTITE%20ECCOBOND%20DS%206601-EN.pdf. |
Stober et al., Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range, Journal of Colloid and Interface Science, vol. 26, Jan. 1968, pp. 62-69, Elsevier Inc., Amsterdam. |
AUS920170084US1, Appendix P; List of IBM Patents or Applications Treated as Related, Mar. 20, 2018, 2 pages. |
Appendix P; List of IBM Patent or Applications Treated as Related, Jul. 25, 2017, 2 pages. |
U.S. Appl. No. 15/590,676, to Eric J. Campbell et al., entitled, Light Emitting Shell in Shell Microcapsules, filed May 9, 2017, assigned to International Business Machines Corporation. |
Yamaura et al., Preparation and characterization of (3-aminopropyl) triethoxysilane-coated magnetite nanoparticles, Journal of Magnetism and Magnetic Materials, vol. 279, Issues 2-3, Aug. 2004, pp. 210-217, ScienceDirect.com (online), Elsevier B.V., Amsterdam. |
Kreft et al., Shell-in-Shell Microcapsules: A Novel Tool for Integrated, Spatially Confined Enzymatic Reactions, Angewandte Chemie, Int. Ed., Jul. 2007 (online Jun. 2007), vol. 46, Issue 29, pp. 5605-5608, Wiley-VCH Verlag GmbH & Co., KGaA, Weinheim, DOI: 10.1002/anie.200701173. |
Xiong et al., Towards Theranostic Multicompartment Microcapsules: in-situ Diagnostics and Laser-induced Treatment, Theranostics, vol. 3, Issue 3, Feb. 2013, pp. 141-151, Ivyspring International, Sydney, Australia. |
Parakhonskiy, Colloidal micro- and nano-particles as templates for polyelectrolyte multilayer capsules, Advances in Colloid and Interface Science, May 2014, vol. 207, pp. 253-264, ScienceDirect.com (online), Elsevier B.V., Amsterdam. |
U.S. Appl. No. 15/299,257, to Eric J. Campbell et al., entitled, Tamper Resistant Electronic Devices, assigned to International Business Machines Corporation, 30 pages. |
U.S. Appl. No. 15/080,120, to Gerald K. Bartley et al., entitled, Secure Crypto Module Including Optical Glass Security Layer, assigned to International Business Machines Corporation, 41 pages. |
Caruso et al. “Robust, Double-Walled Microcapsules for Self-Healing Polymeric Materials,” ACS Applied Materials & Interfaces, 2010, vol. 2, No. 4, pp. 1195-1199. |
Engineering ToolBox, (2003). Specific Heat of some common Substances. [online] Available at: https://www.engineeringtoolbox.com/specific-heat-capacity-d_391.html [Accessed Jan. 9, 2020]. |
List of IBM Patents or Patent Applications Treated as Related, Jan. 16, 2020, 2 pages. |
Number | Date | Country | |
---|---|---|---|
20180340850 A1 | Nov 2018 | US |