Use of self-assembled nanoporous glass colloids for prolongation of plasticity of polymeric materials

Abstract

This invention describes the encapsulation of and self-assembly of meso (nano) porous silica particles from inorganic an inexpensive silica precursor, sodium silicate. The particles have a well defined shape, high surface area, and high uniformity of the pore size, the properties that are typically found for high quality mesoporous material synthesized from organic silica precursors. The disclosure illustrates a synthesis of hard spheres, discoids, and a mixture comprising discoids, gyroids and fibers, termed as origami.

Claims

1. A method of preparing nanoporous silica particles which prolong the plasticity of a polymer material after being added to the said polymer material, the nanoporous silica particles comprising nanoporous silica fibers, nanoporous silica discoids, or a mix of nanoporous silica fibers and nanoporous silica discoids, the method comprising the steps of: combining an inorganic silica precursor, sodium silicate, with an aqueous solvent, an acidic catalyst, and a structure directed agent (SDA) to form a precursor solution; creating, using said precursor solution and a molecular self-assembly process, particles chosen from nanoporous silica fibers, nanoporous silica discoids, and/or a mixture of nanoporous silica fibers and discoids, said nanoporous silica fibers and/or discoids having a porosity in the range of 2-10 nanometers, and having a surface area greater than 500 m.sup.2/gram, wherein said molecular self-assembly process is carried out using a molar sol composition: 1 mol Na.sub.2SiO.sub.3.9H2O:X mol cetyltrimethylammonium bromide (“CTAB”):Y mol HCl:Z mol H.sub.2O; calcining the obtained particles; and adding and retaining a plasticizer inside one or more pores of said nanoporous silica fibers and/or discoids, wherein capture within said one or more pores prolongs plasticity of said polymer material, and wherein X is chosen as any from a range of approximately 0.5-3 mol, and Y is chosen as any from a range of approximately 10-70 mol, and Z is chosen as any from a range of approximately 600-800 mol.

2. The method of claim 1 wherein said structure directed agent (SDA) is an ionic surfactant, a copolymer surfactant, or a mixture of ionic and copolymer surfactants.

3. The method of claim 1, wherein said precursor solution further comprises condensation catalyst, the condensation catalyst selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and a combination thereof.

4. The method of claim 1, wherein said molecular self-assembly process is performed at room temperature (15-25 degrees C.) to synthesize fibers.

5. The method of claim 1, wherein said molecular self-assembly process is performed at 60-90 degrees C. temperature to synthesize discoids.

Description

DESCRIPTION OF THE DRAWINGS

(1) These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings where:

(2) FIG. 1(A) illustrates an scanning electron microscopy (SEM) image of a mixture of mesoporous silica fibers synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729 H2O at 25° C., 24 hours;

(3) FIGS. 1 (B) and (C) illustrate mesoporous silica discoids synthesized from the same sol but at a range between 70° C. and 90° C., 24 h;

(4) FIG. 1(D) illustrates calcined discoids;

(5) FIG. 2 illustrates the x-ray diffraction (XRD) pattern of the mesoporous silica fibers (A) and discoids (B) synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729 H2O, at 25° C., 24 h and 70° C., 24 hours, respectively.

(6) FIG. 3(A) and FIG. 3(B) illustrate transmission electron microscopic (TEM) images of the fibers (A) and discoids (B), showing the internal circular architecture and pore channels running around the particle axis.

(7) FIG. 4 illustrates N2 adsorption/desorption isotherm measured at 77 K on calcined mesoporous silica fibers synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729 H2O at 25° C., 24 hours, with inset (B) illustrating the pore size distribution for the discoids;

(8) FIG. 5 illustrates N2 adsorption/desorption isotherm measured at 77 K on calcined mesoporous silica discoids synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729 H20 at 70° C., 24 hours, with insets (B) illustrating the pore size distribution for the discoids;

(9) FIG. 6 illustrates confocal laser microscopy images at different magnifications of the dye filled mesoporous silica discoids synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729 H20:0.002 R6G at 70° C., 24 h with inset (B) illustrating a magnified image showing the coiled silica tubes forming discoids;

(10) FIGS. 7 (A)-(B) illustrate optical images of the as-synthesized and calcined spheres obtained from the sol of molar composition 1Na2SiO3.9H20:21.69 HCHO:0.51 CTAC:210 H2O with the inset (C) in illustrating the scanning electron microscopy (SEM) image of an individual broken sphere;

(11) FIGS. 7 (D) and (E) illustrate the transmission electron microscopic (TEM) images of the spheres;

(12) FIGS. 8 (A)-(C) illustrate the x-ray diffraction (XRD) patterns of the spheres, discoids and origami particles synthesized from the sols of molar compositions 1Na2SiO3.9H20:5.21-31.51 HCHO:0.56-0.77 CTAC:210 H2O; 1Na2SiO3.9H20:0.56-0.77 CTAC:210 H2O:16.35 HCl, and 1Na2SiO3.9H20:5.21-31.51 HCHO:0.56-0.77 CTAC:210 H2O:16.35 HCl, respectively.

(13) FIGS. 9 (A) and (B) illustrate the confocal microscopy images of discoids and origami particles synthesized from the sols of molar 1Na2SiO3.9H20:0.56-0.77 CTAC:210 H2O:16.35 HCl and 1Na2SiO3.9H20:5.21-31.51 HCHO:0.56-0.77 CTAC:210 H2O:16.35 HCl, respectively, with insets in the images displaying individual particles;

(14) FIG. 10 illustrates a cross-sectional transmission electron microscopic (TEM) image of the gyroids particle synthesized from the sol of molar composition 1Na2SiO3.9H20:0.56-0.77 CTAC:210 H2O:16.35 HCl;

(15) FIG. 11 illustrates a N2 adsorption/desorption plot;

(16) FIG. 12 illustrates an SEM image of parallel nanochannels in fiber like ANSC of uniform shape; and

(17) FIG. 13 illustrates SEM images of self-assembled nano-glass fiber-capsules.

DESCRIPTION

(18) In this invention we use existing plasticizers encapsulated inside nanoporous glass colloids. Such encapsulation protects the plasticizers from deterioration, limits their bio-availability. Such particles are described in a number of publications and patent applications including S. P. Naik, Igor Sokolov, “Room Temperature Synthesis of Nanoporous Silica Spheres and their Formation Mechanism” Solid State Communications, 2007 Volume 144. Issues 10-11, December 2007, Pages 417-440: S. P. Naik, S. P, Elangovan T. Okubo, and Igor Sokolov “Morphology Control of Mesoporotes Silica Particles”. Journal of Physical Chemistry (C), v. 111, n. 30, pp. 11168-11173, 2007: Sokolov, I. and Y. Kievsky, 3D Design of Self Assembled. Vanoporous Colloids. Studies in Surface Science and Catalysis, 2005 v. 156, pp. 433-443, 2005); Ya. Kievsky and I. Sokolov Self-Assembly of uniform Nanoporous Silica Fibers, IEEE Transactions on Nanotechnology, v. 4 (5), pp. 490-494; Sokolov, Ya. Kievsky, “Self-Assembly of Nanoporous Silica Fibers of Uniform Shape”, approved as pending in December 2004 U.S. 60/631,224. All of the above references are hereby incorporated herein by reference.

(19) In principle encapsulation of plasticizers could be done with any capsules. However, it would be economically advantageous to so with ones made with sodium silicate. Below is described is the synthesis of tnesoporous silica shapes using sodium silicate as a silica source.

(20) The particles fibers and mechanically robust and have enough empty area inside of the cylindrical porous to keep plasticizers inside. Examples of such particles are shown in FIGS. 12 and 13

(21) The top portion of FIG. 12 illustrates the SEM image of parallel nanochannels in fiber like ASNC of uniform shape. A large area (left bar-size is 22 gm) and zoom to a few ASNC (right, bar-size is 5 gm). The middle portion illustrates a TEM image of near the ASNC edge showing periodicity about 3.6 nm (left), a schematics showing the arrangement of nanochannels in silica matrix (right). Bottom Portion: XRD of the ASNCs flat) and distribution of the inner tube diameters (right) [V. V. Kievsky, B. Carey, S. Naik, N. Mangan, D. ben-Avraharn, and I. Sokolov, J. Chem. Phys. 128, 151102 (2008) hereby incorporated herein by reference].

(22) FIG. 12, illustrates SEM images of self assembled nanoporous glass fiber capsules. FIGS. 12 (a) and (b) illustrate examples of different syntheses (bar size is 11 pm.

(23) The use of the above silica colloids/fibers strengthens the material. Therefore the amount of encapsulated plasticizer can be increased and consequently, results in the further extension of the plasticizing action. In addition due to decreased bio degradation of the degradation of the plasticizers antibacterial substances can be added inside the same capsules.

(24) Herein we disclose of the synthesis of a procedure nanoporous silica particles of various shapes using sodium silicate (disodium trioxosilicate is a particular example) as a silica source as an economical choice to use micrometer-sized meso (nano) porous silica particles in various shapes from an inexpensive inorganic silica precursor, sodium silicate. It is a robust process. We demonstrate that by adjusting the reaction sol composition, hard spheres, discoids or a mixture of various shapes, termed as origami, comprising gyroids, fibers and discoids can be obtained. The description below uses numbers as exemplary values.

Example 1: Synthesis of Fibers and Discoids

(25) Mesoporous silica fibers and discoids are synthesized using disodium trioxosilicate (Na2SiO3.9H20) as the silica source; cetyltrimethylammonium chloride (or bromide) (CTAC, 25% aqueous) as an example of the structure directed agent (SDA) in the presence of hydrochloric acid as an example of a catalyst. The molar sol composition is at the range of 1Na2SiO3.9H20:0.5-3 CTAC:10-70 HCl:600 800H20. For the example given below, it is fixed at, 1Na2SiO3.9H20:1.5 CTAC:28 HCl:730H20. Typically, 1.6 g of Na2SiO3.9H20 is dissolved in 55.2 g H2O, taken in a high density polypropylene (HD-PP) bottle, understirring for 15 minutes. Separately, 16 g of concentrated HCl is slowly added to 11.2 g CTAC taken in HD-PP bottle and stirred for 2 minutes. The clear sodium silicate solution is then slowly added to CTAC/HCl solution and stirred for 5 minutes. The resulting sol is maintained at fixed temperature ±15° C.+70° C., depending on the desired ratio between the fibers and discoids) for 3-24 hours under quiescent conditions. The product is recovered either by filtration (for example, using a Buckner funnel under vacuum) or by centrifugation, then washed several times with distilled water, and subsequently, dried at for several hours. Depending on the desired applications, the as-synthesized discoids can be used directly, or calcined through a procedure known to one skilled in art. To characterize the particles, the powder x-ray diffraction (XRD) patterns on the particles are collected on a Bruker D8 X-Ray diffractometer using Cuka radiation (40 kV, 40 mA). The scanning electron microscopy (SEM) images are collected on a JEOL 6300 instrument operating at 15 kV. Prior to the measurements, the samples are coated with gold for 1 minute in an Amatech hummer 6.2 sputtering system operating at 40 millitorr. The transmission electron microscopic (TEM) images of the calcined particles are recorded on a JEM 2010 electron microscope (JEOL) at an acceleration voltage of 200 kV. The samples are prepared by dispersing the calcined material in water at room temperature. A few drops of this dispersion were placed on a holey carbon-coated mesh and dried at room temperature. The N2 adsorption/desorption isotherms of the calcined mesoporous silica samples are measured at 77 K on a NOVA 1200e instrument (Quantachrome Co.). Before the measurement, samples are degassed at 350° C. and 10 Pa for at least 12 h. The confocal laser microscopy images of the fluorescent particles are taken on a Nikon, D-Eclipse C1-Microscope. Rhodamine 6G (R6G, Exciton) fluorescent dye filled mesoporous silica discoids are prepared from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729H20:0.002 R6G, that is the same as above, except for the addition of the dye. The dye is at first dissolved in water together with sodium silicate and the resulting solution is added to CTAC/HCl sol, as described above.

(26) The morphology of the synthesized mesoporous silica particles is strongly dependent upon the molar composition of the synthesis sol used in this example. The mostly well-formed fibers of varying sizes as shown in the scanning electron microscopy (SEM) image of FIG. 1 (A) are obtained at room temperature from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:7301120. We have observed that this low curvature fibers begins to disappear with concomitant formation of high curvature and well-formed, single-crystal like 3-5 pm sized discoids upon increasing the synthesis temperature [See FIGS. 1 (B)-(C)] and eventually the fiber to discoid transformation is complete at synthesis temperatures between 60 to 90° C.

(27) FIG. 1 illustrates scanning electron microscopy (SEM) images of (A) mixture of mesoporous silica fibers synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729 H.sub.2O at 25° C., 24 hours and FIGS. 1 (B) and (C) illustrate mesoporous silica discoids synthesized from the same sol but at a range between 70 C and 90° C., 24 h (D) calcined discoids.

(28) The hexagonal p6mm structure of the fibers and discoids is established from x-ray diffraction (XRD) measurement as illustrated by the patterns in FIGS. 2 (A) and (B), respectively. The d100 spacing of ca. 46 A and 47 A was obtained for fibers and discoids, respectively. Calcination at up to 500° C. does not have any noticeable effect on the morphology of the particles as confirmed by the scanning electron microscopy (SEM) images of as-formed and calcined discoids illustrated in FIGS. 1 (C) and (D), respectively.

(29) FIG. 2 illustrates an x-ray diffraction (XRD) pattern of the mesoporous silica fibers (A) and discoids (B) synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729 H2O, at 25° C., 24 hours and 70° C., 24 hours, respectively.

(30) The pore architecture in the particle mesostructure is established from the transmission electron microscopic (TEM) images for fibers and discoids shown in FIG. 3. These images present a well-organized, hexagonal, p6mm structure with hexagonally organized pores and possess a circular architecture with pore channels running around the fiber or discoid axis endowing self-sealed structure to the particles. The diameter of the channels obtained from transmission electron microscopic (TEM) was found to be well in agreement with that obtained from N2 adsorption/desorption measurement vide infra.

(31) FIG. 3 illustrates transmission electron microscopic (TEM) images of the fibers (A) and discoids (B), showing the internal circular architecture and pore channels running around the particle axis. The mesoporous silica fibers and discoids were synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729H20 at 25° C., 24 hours and 70° C., 24 hours, respectively. The insets here are the schematics of fibers and discoids, respectively.

(32) A nitrogen adsorption/desorption measurement conducted at 77.3 K on the calcined fibers and discoids gives type IV isotherms as shown in FIGS. 4 and 5, respectively.

(33) There is little difference between the texture properties of fibers and discoids. Both the isotherms showed a step rise at −0.2 P/Po with little hysteresis, that is typical of high quality mesoporous materials. The mesopore size is estimated, see FIGS. 4 (B) and 5 (B), from the adsorption branch of the isotherm according to the correlation obtained from Nonlinear Fluctuation-Dissipation Theorem (NLDFT) theory. See A. V. Neimark et al., and M. Jaroniec et al., both listed in the reference list below and both hereby incorporated herein by reference. For fibers and discoids, the BET surface areas are 1330 and 1250 m.sup.2/g; mesopore diameters are 2.4 nm and 2.5 nm, and pore volumes are 0.93 cm.sup.3 and 0.96 cm.sup.3/g, respectively.

(34) FIG. 4 illustrates N2 adsorption/desorption isotherm measured at 77 K on calcined mesoporous silica fibers synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729 H.sub.2O at 25° C., 24 h. Inset (B) illustrates the pore size distribution for the discoids.

(35) FIG. 5 illustrates N2 adsorption/desorption isotherm measured at 77 K on calcined mesoporous silica discoids synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:281-1Cl:729H20 at 70° C., 24 h. Inset (B) illustrates the pore size distribution for the discoids.

(36) To elucidate further, the coiling of fibers, the R6G dye loaded discoids are observed by confocal laser microscopy. These images, illustrated in FIG. 6, confirm the coiled macroscopic domains in the discoids as shown by the bright fluorescence of the curled up coiled rods, indicated by arrows in FIG. 6 (B). This result is also in agreement with the scanning electron microscopy (SEM) and transmission electron microscopic (TEM) observations. Moreover, higher temperature promotes formation of curved fibers by balancing free energy of the fibers with the entropic term as reported earlier See Y. Kievsky et al. and I. Sokolov et al. both listed in the reference list below and both hereby incorporated herein by reference.

(37) FIG. 6(A) illustrates confocal laser microscopy images at different magnifications of the dye filled mesoporous silica discoids synthesized from the sol of molar composition 1Na2SiO3.9H20:1.5 CTAC:28 HCl:729H20:0.002 R6G at 70° C., 24 hours. Inset (B) is a magnified image illustrating the coiled silica tubes forming discoids.

(38) Thus, the method described above synthesizes mesoporous single-crystal like with hexagonally organized pores and possess a circular architecture with pore channels running around the fiber or discoid endowing self-sealed-type structure to the particles. For fibers and discoids of this Example 1, the BET surface areas are 1330 m.sup.2/g and 1250 m.sup.2/g; mesopore diameters are 2.4 nm and 2.5 nm, and pore volumes are 0.93 cm.sup.3 and 0.96 cm.sup.3/g, respectively.

Example 2: Synthesis of Spheres, Discoids, Fibers

(39) In this Example 2, mesoporous silica particles are synthesized by using disodium trioxosilicate (Na2SiO3.9H20, Fishcer Scientific) as the silica source, cetyltrimethylammonium chloride (CTAC, 25% aqueous, Aldrich) as an example of the structure directed agent (SDA) in the presence or absence of formamide (Aldrich) and hydrochloric acid (J T Baker) as a catalyst.

(40) Mesoporous silica spheres can be synthesized in the absence of HCl from sols of molar compositions 1Na2SiO3.9H20:5-32 HCHO:0.5-0.8 CTAC:210 H2O; spheres exemplified here are prepared from the sol of molar composition 1Na2SiO3.9H20:22 HCHO:0.5 CTAC:210 H2O.

(41) For the synthesis of discoids, the molar composition of the sol is maintained at 1Na2SiO3.9H20:0.5-0.8 CTAC:210 H2O:16 HCl; whereas, origami shapes are synthesized from the sol of molar composition 1Na2SiO3.9H20:5-32 HCHO:0.5-0.8 CTAC:210 H2O:16 HCl.

(42) A calculated amount of Na2SiO3.9H20 is dissolved in distilled water under stirring for 15 minutes, CTAC solution is then slowly added, followed by the addition of HCHO and/or HCl, whenever required. The stirring is continued for another several minutes. The clear sol thus formed is maintained at room temperature, without stirring, for duration of between several hours to one week. The product is recovered either by filtration (for example, using a Buckner funnel under vacuum) or by centrifugation, then washed several times with distilled water, and subsequently, dried for several hours. Depending on desired applications, the as-synthesized discoids can be used directly, or calcined through a procedure known to one skilled in art.

(43) To characterize the collected product, the powder x-ray diffraction (XRD) patterns on the as-synthesized materials are collected on an MO3X-HF (Bruker AXS) instrument using CuKa radiation (40 kV, 40 mA). The scanning electron microscopy (SEM) images are collected on a JEOL 6300 instrument operating at 15 Kv. Prior to the measurements, the samples are coated with gold for 1 minute in an Anatech hummer 6.2 sputtering system operating at 40 millitorr. The transmission electron microscopic (TEM) images of the calcined particles are recorded on a JEM 2010 electron microscope (JEOL) at an acceleration voltage of 200 kV.

(44) The samples for characterization are prepared by dispersing the calcined material in water at room temperature. A few drops of this dispersion were placed on a holey carbon-coated mesh and dried at room temperature. Dynamic light scattering (DLS) measurements on the sol are performed using BIC model 90Plus Particle Size Analyzer at 20° C. Optical microscopy, scanning electron microscopy (SEM) and transmission electron microscopic (TEM) images of the as-synthesized and calcined spheres synthesized from the sol of molar composition 1Na2SiO3.9H20:21.69 HCHO:0.51-CTAC:210 H2O, are illustrated in FIGS. 7 (A)-(B), 7 (C), and (D,E), respectively.

(45) There is no obvious change in the morphology of the spheres after calcination. However, a few spheres have been found to be damaged or broken, as illustrated in the inset scanning electron microscopy (SEM) image of FIG. 7 (C). The average size of the spheres was ca. 4-6 p.m. The spheres are hard and have a dense internal structure as confirmed from the transmission electron microscopic (TEM) image in FIG. 7 (D). The mesoporous structure in the surface of the sphere is confirmed from the transmission electron microscopic (TEM) image illustrated in FIG. 7 (E). Although spheres can be synthesized under a range of molar compositions 1Na2SiO3.9H20:5-32 HCHO:0.5-0.8 CTAC:210 H2O, their size and distribution is strongly dependent on the sol's molar composition. For example, doubling the amount of formamide will decrease the average diameter of the spheres by −2 pm.

(46) The mesoporous structure of the spheres is confirmed from the x-ray diffraction (XRD) pattern illustrated in FIG. 8 (A). The dio-spacing of ca. 44 A is obtained, corresponding to the hexagonal p6mm structure.

(47) FIG. 7 (A)-(B) illustrate the scanning electron microscopy (SEM) images of the as-synthesized and calcined spheres obtained from the sol of molar composition 1Na2SiO3.9H20:21.69 HCHO:0.51 CTAC:210 H2O. Figure (C) and (D) are the transmission electron microscopic (TEM) images of the spheres. The inset in FIG. 7(B) is the scanning electron microscopy (SEM) image of an individual broken sphere.

(48) FIGS. 8 (A)-(C) illustrate the x-ray diffraction (XRD) patterns of the spheres, discoids and origami particles synthesized from the sols of molar compositions 1Na2SiO3.9H20:5-32 HCHO:0.5-0.8 CTAC:210 H2O; 1Na2SiO3.9H20:0.5-0.8 CTAC:210 H2O:16 HCl, and 1Na2SiO3.9H20: 5-32 HCHO:0.5-0.8 CTAC:210 H2O:16 HCl, respectively.

(49) The discoids and origami particles obtained here have been employed for encapsulating florescent dyes in the mesochannels channels. The confocal microscopy images of these particles are illustrated in FIGS. 9 (A) and (B), respectively. The strong fluorescence radiated by these particles is very clear from these images. The morphologies of the discoid and some of the origami particles are also shown as insets of the FIGS. 9(A) and (B), respectively.

(50) The hexagonal p6mm structure of the discoids and origami particles is confirmed from their x-ray diffraction (XRD) patterns shown in FIGS. 8 (B) and (C), respectively.

(51) The dio-spacings of ca. 47 A and 45 A is obtained for gyroids and origami, respectively.

(52) As confirmed from the cross-sectional transmission electron microscopic (TEM) image illustrated in FIG. 10 of the discoids, the mesoporous channels indeed run in circular or concentric fashion.

(53) FIGS. 9 (A) and (B) illustrate the confocal microscopy images of discoids and origami particles synthesized from the sols of molar 1Na2SiO3.9H20:0.5-0.8 CTAC:210 H2O:16 HCl and 1Na2SiO3.9H20:5-32 HCHO:0.5-0.8 CTAC:210 H2O:16 HCl, respectively. The insets in the images of FIG. 9(B) display individual particles.

(54) FIG. 10 illustrates the cross-sectional transmission electron microscopic (TEM) image of the gyroids particle synthesized from the sol of molar composition 1Na2SiO3.9H20:0.5-0.8 CTAC:210 H2O:16 HCl.

(55) BET (gas absorption) measurements, illustrated in FIG. 11, demonstrate that bulk mesoporous material has been produced. FIG. 11 is a N2 adsorption/desorption plot (the type of the plot is indicative of mesoporous material).

(56) From the above measurements, one can find that for the spheres, the surface area of the spheres is at least 600 m.sup.2/g, the pore diameter and pore volumes are 3.3 nm, and 0.3 cm.sup.3/g, respectively. For discoids and origami, the surface areas of the particles is at 500900 m.sup.2/g, where as the pore diameter and volume were in the range of 2.4-3.3 nm, and 0.2-0.4 cm.sup.3/g, respectively.

(57) The particles synthesized by the processes described can be used: as a filler for chromatography columns; for slow release of various chemicals (slow drug release) or as absorbents for various chemicals such as antibacterial agents, anti-rusting, or glue for self-healing materials, etc.

(58) The illustrative embodiments and modifications thereto described hereinabove are merely exemplary. It is understood that other modifications to the illustrative embodiments will readily occur to persons of ordinary skill in the art. All such modifications and variations are deemed to be within the scope and spirit of the present invention as will be defined by the accompanying claims.

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