Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
  • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
  • B01J20/282—Porous sorbents
  • B01J20/283—Porous sorbents based on silica
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
  • B01J20/28004—Sorbent size or size distribution, e.g. particle size
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
  • B01J20/282—Porous sorbents
  • B01J20/285—Porous sorbents based on polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
  • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
  • B01J20/3204—Inorganic carriers, supports or substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
  • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
  • B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3234—Inorganic material layers
  • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
  • B01J20/3244—Non-macromolecular compounds
  • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
  • B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3289—Coatings involving more than one layer of same or different nature
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
  • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated

Definitions

• Superficially porous particles also called pellicular, fused-core, or core-shell particles
• These earlier superficially porous materials had thin porous layers, prepared from the adsorption of silica sols to the surface of ill-defined, polydisperse, nonporous silica cores (>20 ⁇ ). The process of spray coating or passing a solution of sols through a bed of particles was commonly used.
• Kirkland extensively explored the use of superficially porous particles throughout this time and helped develop the Zipax brand of superficially porous materials in the 1970's. A review of Kirkland' s career was provided by Unger (Journal of Chromatography A, 1060 (2004) 1).
• Narrow distribution superficially porous particles have been reported by Kirkland (US Application 20070189944) using a Layer-by- Layer approach (LBL) - however these particles are not highly spherical.
• LBL Layer-by- Layer approach
• Other surfactant-templated approaches can yield low yields of narrow distribution, fully porous particles, however these approaches have not been used to prepare monodisperse, spherical superficially porous particles having chromatographically enhanced pore geometry.
• Modern, commercially available superficially porous particles use smaller ( ⁇ 2 ⁇ ), monodisperse, spherical, high purity non-porous silica cores.
• a porous layer is formed, growing these particles to a final diameter between 1.7-2.7 ⁇ .
• the thickness of the porous layer and pore diameter are optimized to suit a particular application (e.g., small vs. large molecule separations).
• these material are calcined (500-1000°C in air). Additional pore enlargement, acid treatment, rehydroxylation, and bonding steps have been reported.
• these reported superficially porous particle processes differ, they can be classified as layering of preformed sols (e.g., AMT process) or growth using high purity tetraalkoxysilane monomers (e.g., the University of Cork process).
• the AMT and University of Cork processes are similar in that they incorporate a repeated in-process workup (over nine times) using centrifugation followed by redispersion.
• the AMT process this is a requirement of the layer-by-layer approach, in which alternate layers of positively charged poly-electrolyte and negatively charged silica sols are applied.
• the in-process workup is used to reduce reseeding and agglomeration events.
• Particles prepared by this approach have smooth particle surfaces and have notable layer formation by FIB/SEM analysis. While both approaches use similar spherical monodisperse silica cores that increase in particle size as the porous layer increases, they differ in final particle morphology of the superficially porous particle.
• the AMT process as shown in Figure 8, results in bumpy surface features and variation of the porous layer thickness. This difference in surface morphology may be due to variation in the initial layering of sols.
• both processes use high temperature thermal treatment in air to remove additives (polyelectrolyte or surfactants) and improve the mechanical properties of their superficially porous particles. Since hybrid materials are not thermally stable above 600°C, this approach is not applicable to the formation of hybrid superficially porous particles.
• narrow particle size distribution porous chromatographic particles is expected to have great benefit for chromatographic separations. Such particles should have an optimal balance of column efficiency and backpressure. While the description of monodisperse superficially porous silica particles has been noted in the literature, these particles do not display chromatographically enhanced pore geometry and desirable pore diameters for many chromatographic applications. Thus, there remains a need for a process in which narrow particle size distribution porous materials can be prepared with desirable pore diameters and chromatographically enhanced pore geometry. Similarly, there remains a need for a process in which narrow particle size distribution porous materials can be prepared with improved chemical stability with high pH mobile phases.
• the invention provides a superficially porous material comprising a substantially nonporous core and one or more layers of a porous shell material surrounding the core.
• the material of the invention is comprised of superficially porous particles. In other embodiments the material of the invention is comprised of a superficially porous monolith.
• the material of the invention has a substantially narrow particle size distribution.
• the 90 / w ratio of particle sizes of the material is from 1.00-1.55; from 1.00-1.10 or from 1.05-1.10.
• the core has a substantially narrow particle size distribution.
• the 90 / w ratio of particle sizes of the core is from 1.00-1.55; from 1.00-1.10 or from 1.05-1.10.
• the material of the invention has chromato graphically enhancing pore geometry.
• the material of the invention has a small population of micropores.
• the substantially nonporous core material is silica; silica coated with an inorganic/organic hybrid surrounding materia; a magnetic core material; a magnetic core material coated with silica; a high thermal conductivity core material; a high thermal conductivity core material coated with silica; a composite material; an inorganic/organic hybrid surrounding material; a composite material coated with silica; a magnetic core material coated with an inorganic/organic hybrid surrounding material; or a high thermal conductivity core material coated with an inorganic/organic hybrid surrounding material.
• the composite material comprises a magnetic additive material or a high thermal conductivity additive or a combination thereof.
• the porous shell material is a porous silica; a porous composite material; or a porous inorganic/organic hybrid material.
• each layer is independently selected from is a porous inorganic/organic hybrid material, a porous silica, a porous composite material or mixtures thereof.
• the substantially nonporous core is a composite material and the porous shell material is a porous silica.
• the substantially nonporous core is a composite material and the porous shell material is a porous inorganic/organic hybrid material. In still other embodiments, the substantially nonporous core is a composite material and the porous shell material is a composite material.
• the substantially nonporous core is silica and the porous shell material is a porous composite material.
• the substantially nonporous core is a silica and the porous shell material is a porous inorganic/organic hybrid material.
• the substantially nonporous core is a magnetic core material and the porous shell material is a porous silica.
• the substantially nonporous core is a magnetic core material and the porous shell material is a porous inorganic/organic hybrid material.
• the substantially nonporous core is a magnetic core material and the porous shell material is a composite material.
• the substantially nonporous core is a high thermal conductivity core material and the porous shell material is a porous silica.
• the substantially nonporous core is a high thermal conductivity core material and the porous shell material is a porous inorganic/organic hybrid material.
• the substantially nonporous core is a high thermal conductivity core material and the porous shell material is a composite material.
• the porous inorganic/organic hybrid shell material has the formula:
• R and R are each independently Ci-Ci 8 alkoxy, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl, C 2 -C 18 alkenyl, C 2 -Ci 8 alkynyl, C 3 -Ci 8 cycloalkyl, Ci-Ci 8 heterocycloalkyl, C 5 -Ci 8 aryl, C 5 -Ci 8 aryloxy, or C 1 -C18 heteroaryl;
• R 2 is C 1 -C18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C C 18 heterocycloalkyl, Cs-Ci 8 aryl, Ci-Ci 8 heteroaryl; or absent; wherein each R 2 is attached to two or more silicon atoms;
• p and q are each independently 0.0 to 3.0
• t is 0.5, 1.0, or 1.5;
• d is 0 to about 30;
• n is an integer from 1-20; wherein R, R 1 and R 2 are optionally substituted;
• the porous inorganic/organic hybrid shell material has the formula:
• R and R are each independently Ci-Ci 8 alkoxy, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, C 3 -Ci 8 cycloalkyl, Ci-Ci 8 heterocycloalkyl, C 5 -Ci 8 aryl, C 5 -Ci 8 aryloxy, or C 1 -C18 heteroaryl;
• d is 0 to about 30;
• the porous inorganic/organic hybrid shell material has has the formula:
• R 1 is C 1 -C 18 alkoxy, C C 18 alkyl, C C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, Ci-Ci 8 heterocycloalkyl, Cs-Ci 8 aryl, Cs-Ci 8 aryloxy, or Ci-Ci 8 heteroaryl;
• R 2 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C C 18 heterocycloalkyl, C 5 -Ci 8 aryl, Ci-Ci 8 heteroaryl; or absent; wherein each R 2 is attached to two or more silicon atoms;
• d is 0 to about 30;
• n is an integer from 1-20.
• the porous inorganic/organic hybrid shell material has the formula:
• repeat units A, B, and C may be random, block, or a combination of random and block;
• A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;
• B is an organosiloxane repeat unit which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;
• C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond;
• the porous inorganic/organic hybrid shell material has the formula:
• repeat units A, B, B*, and C may be random, block, or a combination of random and block;
• A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;
• B is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond,
• B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization;
• C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond;
• x and y are positive
• each layer is independently selected from is a porous inorganic/organic hybrid material, a porous silica, a porous composite material or mixtures thereof.
• the core of the material of the invention has an increased hybrid content near the surface of the core.
• the core of the material of the invention has a decreased hybrid content near the surface of the core.
• the material of the invention has an increased hybrid content near the surface of the superficially porous material.
• the material of the invention has a decreased hybrid content near the surface of the superficially porous material.
• the composite material comprises a magnetic additive material.
• the magnetic additive material has a mass magnetization at room temperature greater than 15 emu/g.
• the magnetic additive material is a ferromagnetic material.
• the magnetic additive material is a ferrimagnetic material.
• the magnetic additive material is a magnetite; maghemite; yttrium iron garnet; cobalt; Cr0 2 ; a ferrite containing iron and Al, Mg, Ni, Zn, Mn or Co; or a combination thereof.
• the magnetic core material has a mass magnetization at room temperature greater than 15 emu/g.
• the magnetic core material is a ferromagnetic material.
• the magnetic core material is a ferrimagnetic material.
• the magnetic core material is a magnetite; maghemite; yttrium iron garnet; cobalt; Cr0 2 ; a ferrite containing iron and Al, Mg, Ni, Zn, Mn or Co; or a combination thereof.
• the composite comprises a high thermal conductive additive material
• the composite material comprises a magnetic additive material.
• the high thermal conductivity additive is crystalline or amorphous silicon carbide, aluminum, gold, silver, iron, copper, titanium, niobium, diamond, cerium, carbon, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, or an oxide or a nitride thereof, or combinations thereof.
• the high thermal conductivity additive is diamond.
• the high thermal conductivity core material is crystalline or amorphous silicon carbide, aluminum, gold, silver, iron, copper, titanium, niobium, diamond, cerium, carbon, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, or an oxide or a nitride thereof, or combinations thereof.
• the material of the invention has a highly spherical core morphology; a rod shaped core morphology; a bent-rod shaped core morphology; a toroid shaped core morphology; or a dumbbell shaped core morphology.
• the material of the invention has a mixture of highly spherical, rod shaped, bent-rod shaped, toroid shaped or dumbbell shaped core morphologies.
• the material of the invention has a significantly higher thermal conductivity than a fully porous silica particles of the same size. In other embodiments, the material of the invention has a significantly higher thermal conductivity than a superficially porous silica particles of the same size.
• the material of the invention are capable of forming a packed beds with improved permeability as compared to a fully porous silica particles of the same size. In still other embodiments, the material of the invention is capable of forming a packed beds with improved permeability as compared to a superficially porous silica particles of the same size.
• the material of the invention has improved chemical stability to high pH mobile phases as compared to unbonded, fully porous silica particles of the same size. In still other embodiments, the material of the invention improved chemical stability to high pH mobile phases as compared to unbonded, superficially porous silica particles of the same size.
• the core has a particle size of 0.5-10 ⁇ ; 0.8-5.0 ⁇ ; or 1.3-3.0 ⁇ .
• each porous layer is independently from 0.05 ⁇ to 5 ⁇ . in thickness as measured perpendicular to the surface of the nonporous core; from 0.06 ⁇ to 1 ⁇ . in thickness as measured perpendicular to the surface of the nonporous core; or from 0.20 ⁇ to 0.70 ⁇ . in thickness as measured perpendicular to the surface of the nonporous core.
• the materials of the invention have an average particle size between 0.8-10.0 ⁇ ; between 1.1-5.0 ⁇ ; or between 1.3-2.9 ⁇ .
• the materials of the invention have pores having an average diameter of about 25-600 A; about 60-350 A; about 80-300 A; or about 90-150 A.
• the materials of the invention have an average pore volume of about 0.11-0.50 cm 3 /g; of about 0.09-0.45 cm 3 /g; or of about 0.17-0.30 cm 3 /g.
• the materials of the invention have a pore surface area is between about 10m 2 /g and 400m 2 /g; between about 15m 2 /g and 300m 2 /g; or between about 60m 2 /g and 200m 2 /g.
• the materials of the invention are surface modified.
• the materials of the invention are surface modified by: coating with a polymer; by coating with a polymer by a combination of organic group and silanol group modification; a combination of organic group modification and coating with a polymer; a combination of silanol group modification and coating with a polymer; formation of an organic covalent bond between the material's organic group and a modifying reagent; or a combination of organic group modification, silanol group modification and coating with a polymer.
• the superficially porous material has a smooth surface. In other embodiments of the invention, the superficially porous material has a rough surface. In another aspect, the invention provides a method for preparing a superficially porous material comprising:
• the method for preparing a superficially porous material further comprises the step of :
• the substantially nonporous core material is silica, silica coated with an inorganic/organic hybrid surrounding material, magnetic core material, a magnetic core material coated with silica, a high thermal conductivity core material, a high thermal conductivity core material coated with silica, a composite material, a composite material coated with an inorganic/organic hybrid surrounding material, a composite material coated with silica, a magnetic core material coated with an inorganic/organic hybrid surrounding material, or a high thermal conductivity core material coated with an inorganic/organic hybrid surrounding material.
• each layer of porous shell material wherein each layer is independently selected from is a porous inorganic/organic hybrid material, a porous silica, a porous composite material or mixtures thereof.
• each layer of porous shell material is applied using sols, a polyelectrolyte or a chemically degradable polymer, wherein:
• the sols are inorganic sols, hybrid sols, nanoparticles, or mixtures thereof; and b) the polyelectrolyte or chemically degradable polymer is removed from the material using chemical extraction, degradation, or thermal treatment at temperatures less than 500°C, or combinations thereof.
• each layer of porous shell material is applied by formation through an electrostatic or acid/base interaction of an ionizable group comprising the steps of:
• the prebonding of the substantially nonporous core or sols includes washing with and acid or base, or a charged polyelectrolyte. In other embodiments, the prebonding of the substantially nonporous core or sols includes chemical transformation of an accessible hybrid organic group.
• the accessible hybrid organic group is an aromatic group that can undergo sulfonation, nitration, amination, or chloromethylation followed by oxidation or nucleophillic displacement with amine containing groups to form ionizable groups.
• the accessible hybrid organic group is an alkene group that can undergo oxidation, cross-metathesis, or polymerization to form ionizable groups.
• the accessible hybrid organic group is an thiol group that can undergo oxidation, radical addition, nucleophillic displacement, or polymerization to form ionizable groups.
• the prebonding of the substantially nonporous core or sols includes bonding with an alkoxysilane that has an ionizable group of equation 1,
• x is 0-3; advantageously 0;
• Y represents chlorine, dimethylamino, triflate, methoxy, ethoxy, or a longer chain alkoxy group
• R represent a basic group, including (but not limited to) -NH 2 , -N(R')H, -N(R') 2 , -N(R' )3 + , -NH(CH 2 ) m NH 2, -NH(CH 2 ) m N(R')H -NH(CH 2 ) m N(R') 2, -NH(CH 2 ) m N(R') 3 + , Pyridyl, imidizoyl, polyamine.
• R' independently represents an alkyl, branched alkyl, aryl, or cycloalkyl group
• n 2-6.
• the prebonding of the substantially nonporous core or sols includes bonding with an alkoxysilane that has an ionizable group of equation 2,
• x is 0-3; advantageously 0;
• Y represents chlorine, dimethylamino, triflate, methoxy, ethoxy, or a longer chain alkoxy group
• A represent an acidic group, including (but not limited to) a sulfonic acid, carboxylic acid, phosphoric acid, boronic acid, arylsulfonic acid, arylcarboxylic acid, arylphosphonic acid, and arylboronic acid.
• R' independently represents an alkyl, branched alkyl, aryl, or cycloalkyl group.
• each layer of porous shell material is applied using a polyelectrolyte or a chemically degradable polymer.
• the polyelectrolyte or a chemically degradable is removed from the material by chemical extraction, degradation, or thermal treatment at temperatures less than 500°C, or combinations thereof.
• each layer of porous shell material is applied using alkoxysilanes, organoalkoxysilanes, nanoparticles, polyorganoalkoxysiloxanes, or combinations thereof, comprising the steps of:
• the alkoxysilanes, organoalkoxysilanes, nanoparticles, polyorganoalkoxysiloxanes, or combinations thereof are condensed on the substantially nonporous core in a solution comprising ethanol, water, ammonium hydroxide, an ionic surfactant; and an non-ionic surfactant.
• the ionic surfactant is Cio-C 3 oN(R) 3 + X " , where R is methyl, ethyl, propyl, alkyl, fluoroalkyl; X is a halogen, hydroxide, or of the form R'S0 3 " or R'C0 2 " where R' is methyl, ethyl, butyl, propyl, isopropyl, tert-butyl, aryl, tolyl, a haloalkyl or a fluoroalkyl group.
• the ionic surfactant is octadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide,
• the concentration of ionic surfactant is maintained in the reaction solution between 5-17 mM; or in certain embodiments between 8-14 mM.
• the non-ionic surfactant is a diblock or triblock copolymer.
• the copolymer is (PEO)x(PPO)y(PEO)x,
• PEO is a polyethylene oxide repeat unit
• PPO is a polypropylene oxide repeat unit
• x is an integer between 5-106,
• y is an integer between 30-85.
• the triblock copolymer is Pluronic ® P123, having
• the alkoxysilanes, organoalkoxysilanes, or combinations thereof are condensed on the substantially nonporous core in a solution comprising:
• the alkoxysilane used is selected from the group of tetramethoxsilane or tetraethoxysilane.
• the organosiloxane is selected from the group of phenyltriethoxysilane; phenyltrimethoxysilane; phenylethyltriethoxysilane;
• the alkoxysilane used is tetraethoxysilane and the organoalkoxysilane used is l,2-bis(triethoxysilyl)ethane.
• the concentration of octadecyltrimethylammonium bromide is maintained between 8-14 mM.
• the molar ratio of octadecyltrimethylammonium bromide and Pluronic ® P123 is maintained at or above 1.30.
• the molar ratio of alkoxysilane to organoalkoxysilane ranges between 30: 1 to 1 :30.
• alkoxysilane, organoalkoxysilane, or combinations thereof are prediluted in ethanol.
• prediluted ethanol solutions of alkoxysilane, organoalkoxysilane, or combinations thereof are added at a slow and constant rate to prevent fines generation, aggregation and agglomeration.
• prediluted ethanol solutions of alkoxysilane, organoalkoxysilane, or combinations thereof are added a rate between
• a secondary solution comprising ethanol, water, ammonium hydroxide, ionic surfactant and non-ionic surfactant is added at a slow and constant rate to prevent fines generation, aggregation and agglomeration.
• the secondary solution comprising ethanol, water, ammonium hydroxide, ionic surfactant and non- ionic surfactant is added within a range between the rate required to maintain a uniform ratio of particle surface area (m 2 ) to reaction volume, to the rate required to maintain a uniform ratio of particle volume (m 3 ) to reaction volume.
• the surfactant mixture is removed through one or more of the following; extractions with acid, water, or organic solvent; ozonolysis treatments, thermal treatments ⁇ 500°C, or thermal treatments between 500-1000°C.
• the surfactant mixture is removed through combination of acid extractions and ozonolysis treatments.
• each layer of porous shell material is applied using alkoxysilanes, organoalkoxysilanes, nanoparticles, polyorganoalkoxysiloxanes, or combinations thereof,: comprising the steps of:
• the alkoxysilane used is selected from the group of tetramethoxsilane or tetraethoxysilane.
• the organosiloxane is selected as one or more of the following from the group of phenyltriethoxysilane; phenyltrimethoxysilane;
• phenylethyltriethoxysilane phenylethyltriethoxysilane; phenylethyltrimethoxysilane; ethyltriethoxysilane;
• ethyltrimethoxysilane methyltriethoxysilane; methyltrimethoxysilane, diethyldiethoxysilane; diethyldimethoxysilane l,4-bis(triethoxysilyl)benzene; l,4-bis(trimethoxysilyl)benzene; 1,3- bis(triethoxysilyl)benzene; l,3-bis(trimethoxysilyl)benzene; l,8-bis(triethoxysilyl)octane; 1,8- bis(trimethoxysilyl)octane; l,2-bis(trimethoxysilyl)ethane; l,2-bis(triethoxysilyl)ethane; 1,2- bis(methyldiethoxysilyl)ethane; 1 ,2-bis(methyldimethoxysilyl)ethane; vinyl trie thoxysilane; vinyltrimethoxy
• the alkoxysilane used is tetraethoxysilane and the organoalkoxysilane used is octadecyltrimethoxysilane.
• the alkoxysilane, one or more organoalkoxysilanes, or combinations thereof are prediluted in ethanol.
• the prediluted ethanol solutions of alkoxysilane, one or more organoalkoxysilanse, or combinations thereof are added a slow and constant rate to prevent fines generation, aggregation and agglomeration.
• prediluted ethanol solutions of alkoxysilane, one or more organoalkoxysilanes, or combinations thereof are added a rate between 5-500 ⁇ ⁇ .
• a secondary solution comprising ethanol, water, and ammonium hydroxide is added at a slow and constant rate to prevent fines generation, aggregation and agglomeration.
• a secondary solution comprising ethanol, water, and ammonium hydroxide is added within a range between the rate required to maintain a uniform ratio of particle surface area (m 2 ) to reaction volume, to the rate required to maintain a uniform ratio of particle volume (m 3 ) to reaction volume.
• porosity is introduced through extraction, degradation, hydrolysis, deprotection, or transformation of the hybrid group through one or more of the following; extractions with acid, water, or organic solvent; ozonolysis treatments, thermal treatments ⁇ 500°C, or thermal treatments between 500- 1000°C.
• porosity is introduced through extraction, degradation, hydrolysis, deprotection, or transformation of the hybrid group through combination of acid extractions, ozonolysis treatments and/or thermal treatments ⁇ 500°C.
• each layer is applied using a mixture of formula XX.
• D is one or more inorganic components upon initial condensation
• E is one or more hybrid components upon initial condensation
• the precursor for the inorganic component upon initial condensation (D) is selected from oxide, hydroxide, ethoxide, methoxide, propoxide, isopropoxide, butoxide, sec-butoxide, tert-butoxide, iso-butoxide, phenoxide, ethylhexyloxide, 2-methyl-2-butoxide, nonyloxide, isooctyloxide, glycolates, carboxylate, nitrate, chlorides, and mixtures thereof of silicon, titanium, zirconium, or aluminum.
• the precursor for the inorganic component upon initial condensation (D) is selected from tetraethoxysilane, tetramethoxysilane, methyl titanium triisopropoxide, methyl titanium triphenoxide, titanium allylace to acetate triisopropoxide, titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium trichloride, and zirconium methacryloxyethylacetoacetate tri-n-propoxide.
• the precursor for the hybrid component upon initial condensation (E) is selected from l,2-bis(triethoxysilyl)ethane, 1 ,2-bis(trimethoxysilyl)ethane, 1 ,4-bis(triethoxysilyl)benzene, 1 ,4-bis(trimethoxysilyl)benzene, 1 ,3-bis(triethoxysilyl)benzene, l,3-bis(trimethoxysilyl)benzene, l,3,5-tris(triethoxysilyl)benzene, 1,3,5- tris(trimethoxysilyl)benzene, and bis(4-triethoxysilylphenyl)diethoxysilane.
• the precursor for the hybrid component upon initial condensation that can be further reacted to increase the porosity of the superficially porous layer (F) is selected from phenyltrimethoxysilane, phenyltriethoxysilane,
• acetyloxyethyltrimethoxysilane acetyloxyethyltriethoxysilane; chloroethyltriethoxysilane; chloroethyltrimethoxysilane; methacryloxypropyltrimethoxysilane;
• methacryloxypropyltriethoxysilane bromoethyltrimethoxysilane; bromoethyltriethoxysilane; fluorotriethoxysilane; fluorotrimethoxysilane; and alkoxysilanes of the type:
• R was the corresponding octadecyl, dodecyl, octyl, 2-ethoxyethyl, or 3-ethyl-3-pentyl group
• v was an integer equal to 1- 4,
• porosity is introduced by reaction of hybrid group F through protodesilylation, hydrolysis, deprotection, acid extraction, thermal treatment ⁇ 500 °C, oxidation, ozonolysis or decomposition.
• the methods provide materials in which 1-15 layers are formed in the process. In other aspects, 2 -5 layers are formed. In still other 1-2 layers are formed.
• the superficially porous material is optimized by acid extraction, classification, ozonolysis treatment, hydrothermal treatment, acid treatment or combinations thereof.
• the superficially porous material is further surface modified.
• coating with a polymer coating with a polymer by a combination of organic group and silanol group modification; a combination of organic group modification and coating with a polymer; a combination of silanol group modification and coating with a polymer; formation of an organic covalent bond between the material's organic group and a modifying reagent; or a combination of organic group modification, silanol group modification and coating with a polymer.
• the invention provides a method for increasing the porosity of a substantially nonporous material comprising:
• the invention provides a separations device having a stationary phase comprising the superficially porous material of the invention.
• said device is selected from the group consisting of chromatographic columns, thin layer plates, filtration membranes, microfluidic separation devices, sample cleanup devices, solid supports, solid phase extraction devices, microchip separation devices, and microtiter plates,.
• the separations device is useful for applications selected from the group consisting of solid phase extraction, high pressure liquid chromatography, ultra high pressure liquid chromatography, combinatorial chemistry, synthesis, biological assays, ultra performance liquid chromatography, ultra fast liquid chromatography, ultra high pressure liquid chromatography, supercritical fluid chromatography, and mass spectrometry.
• the separations device is useful for biological assays and wherein the biological assays are affinity assays or ion-exchanged assays.
• the invention provides a chromatographic column, comprising a) a column having a cylindrical interior for accepting a packing material and b) a packed chromatographic bed comprising the superficially porous material of the invention.
• the invention provides a chromatographic device, comprising a) an interior channel for accepting a packing material and
• the invention provides a kit comprising the superficially porous material of the invention, and instructions for use.
• the instructions are for use with a separations device.
• the separations device is selected from the group consisting of chromatographic columns, thin layer plates, microfluidic separation devices, solid phase extraction devices, filtration membranes, sample cleanup devices and micro titer plates.
• Figure 1 is an SEM analysis of Products lh (top) and 11 (bottom) from Example 1.
• Figure 2 is an SEM analysis of Products 5a from Example 5.
• Figure 3 is an SEM analysis of Products l ib from Example 11.
• Figure 4 is an SEM analysis of Products diamond cores (top) and Product 73L1 (bottom) from Example 73.
• Figure 5 is an SEM analysis of Products 74L3 from Example 74.
• Figure 6 is an SEM analysis of Products 76L2 (top) and 77L2 (bottom) from Examples 76 and 77.
• Figure 7 is an SEM (left) and FIB/SEM (middle, right) analysis of selected superficially porous particles from Example 44.
• Figure 8 is an SEM left) and FIB/SEM analysis of HALO (AMT) Superficially porous particles.
• the present invention provides novel chromatographic materials, e.g., for
• the present invention provides novel chromatographic materials, e.g., for
• Hybrid including “hybrid inorganic/organic material,” includes inorganic-based structures wherein an organic functionality is integral to both the internal or “skeletal” inorganic structure as well as the hybrid material surface.
• the inorganic portion of the hybrid material may be, e.g., alumina, silica, titanium, cerium, or "Hybrid” includes inorganic -based structures wherein an organic functionality is integral to both the internal or “skeletal” inorganic structure as well as the hybrid material surface.
• the inorganic portion of the hybrid material may be, e.g., alumina, silica, titanium, cerium, or zirconium oxides, or ceramic material; in an advantageous embodiment, the inorganic portion of the hybrid material is silica.
• exemplary hybrid materials are shown in U.S. Patent Nos. 4,017,528, 6,528, 167, 6,686,035 and 7,175,913 and International Application Publication No. WO2008/103423.
• alicyclic group includes closed ring structures of three or more carbon atoms.
• Alicyclic groups include cycloparaffins or naphthenes which are saturated cyclic hydrocarbons, cycloolefins, which are unsaturated with two or more double bonds, and cycloacetylenes which have a triple bond. They do not include aromatic groups.
• Examples of cycloparaffins include cyclopropane, cyclohexane and cyclopentane.
• cycloolefins include cyclop entadiene and cyclooctatetraene.
• Alicyclic groups also include fused ring structures and substituted alicyclic groups such as alkyl substituted alicyclic groups.
• such substituents can further comprise a lower alkyl, a lower alkenyl, a lower alkoxy, a lower alkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, a hydroxyl, - CF3, -CN, or the like.
• aliphatic group includes organic compounds characterized by straight or branched chains, typically having between 1 and 22 carbon atoms. Aliphatic groups include alkyl groups, alkenyl groups and alkynyl groups. In complex structures, the chains can be branched or cross-linked. Alkyl groups include saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups and branched-chain alkyl groups. Such hydrocarbon moieties may be substituted on one or more carbons with, for example, a halogen, a hydroxyl, a thiol, an amino, an alkoxy, an alkylcarboxy, an alkylthio, or a nitro group.
• lower aliphatic as used herein means an aliphatic group, as defined above (e.g., lower alkyl, lower alkenyl, lower alkynyl), but having from one to six carbon atoms.
• Representative of such lower aliphatic groups, e.g., lower alkyl groups are methyl, ethyl, n-propyl, isopropyl, 2-chloropropyl, n-butyl, sec-butyl, 2-aminobutyl, isobutyl, tert-butyl, 3-thiopentyl and the like.
• alkylamino means an alkyl group, as defined above, having an amino group attached thereto. Suitable alkylamino groups include groups having 1 to about 12 carbon atoms, advantageously from 1 to about 6 carbon atoms.
• alkylthio refers to an alkyl group, as defined above, having a sulfhydryl group attached thereto.
• Suitable alkylthio groups include groups having 1 to about 12 carbon atoms, advantageously from 1 to about 6 carbon atoms.
• alkylcarboxyl as used herein means an alkyl group, as defined above, having a carboxyl group attached thereto.
• alkoxy as used herein means an alkyl group, as defined above, having an oxygen atom attached thereto.
• Representative alkoxy groups include groups having 1 to about 12 carbon atoms, advantageously 1 to about 6 carbon atoms, e.g., methoxy, ethoxy, propoxy, tert-butoxy and the like.
• alkenyl and alkynyl refer to unsaturated aliphatic groups analogous to alkyls, but which contain at least one double or triple bond respectively. Suitable alkenyl and alkynyl groups include groups having 2 to about 12 carbon atoms, advantageously from 1 to about 6 carbon atoms.
• alkyl includes saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkyl groups and cycloalkyl substituted alkyl groups.
• a straight chain or branched chain alkyl has 30 or fewer carbon atoms in its backbone, e.g., C1-C30 for straight chain or C3-C30 for branched chain.
• a straight chain or branched chain alkyl has 20 or fewer carbon atoms in its backbone , e.g., C1-C20 for straight chain or C3-C20 for branched chain, and more advantageously 18 or fewer.
• advantageous cycloalkyls have from 4-10 carbon atoms in their ring structure and more advantageously have 4-7 carbon atoms in the ring structure.
• lower alkyl refers to alkyl groups having from 1 to 6 carbons in the chain and to cycloalkyls having from 3 to 6 carbons in the ring structure.
• alkyl (including “lower alkyl) as used throughout the specification and Claims includes both “unsubstituted alkyls” and “substituted alkyls”, the latter of which refers to alkyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone.
• substituents can include, for example, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl
• aralkyl is an alkyl substituted with an aryl, e.g., having 1 to 3 separate or fused rings and from 6 to about 18 carbon ring atoms, e.g., phenylmethyl (benzyl).
• amino refers to an unsubstituted or substituted moiety of the formula -NRaRb, in which Ra and Rb are each independently hydrogen, alkyl, aryl, or heterocyclyl, or Ra and Rb, taken together with the nitrogen atom to which they are attached, form a cyclic moiety having from 3 to 8 atoms in the ring.
• amino includes cyclic amino moieties such as piperidinyl or pyrrolidinyl groups, unless otherwise stated.
• An “amino-substituted amino group” refers to an amino group in which at least one of Ra and Rb, is further substituted with an amino group.
• aromatic group includes unsaturated cyclic hydrocarbons containing one or more rings.
• Aromatic groups include 5- and 6-membered single-ring groups which may include from zero to four heteroatoms, for example, benzene, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine and the like.
• the aromatic ring may be substituted at one or more ring positions with, for example, a halogen, a lower alkyl, a lower alkenyl, a lower alkoxy, a lower alkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, a hydroxyl, -CF3, -CN, or the like.
• aryl includes 5- and 6-membered single -ring aromatic groups that may include from zero to four heteroatoms, for example, unsubstituted or substituted benzene, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine and the like.
• Aryl groups also include polycyclic fused aromatic groups such as naphthyl, quinolyl, indolyl and the like. The aromatic ring can be substituted at one or more ring positions with such substituents, e.g., as described above for alkyl groups.
• Suitable aryl groups include unsubstituted and substituted phenyl groups.
• aryloxy as used herein means an aryl group, as defined above, having an oxygen atom attached thereto.
• aralkoxy as used herein means an aralkyl group, as defined above, having an oxygen atom attached thereto. Suitable aralkoxy groups have 1 to 3 separate or fused rings and from 6 to about 18 carbon ring atoms, e.g., O-benzyl.
• ceramic precursor is intended include any compound that results in the formation of a ceramic material.
• Chiral moiety is intended to include any functionality that allows for chiral or stereoselective syntheses.
• Chiral moieties include, but are not limited to, substituent groups having at least one chiral center, natural and unnatural amino-acids, peptides and proteins, derivatized cellulose, macrocyclic antibiotics, cyclodextrins, crown ethers, and metal complexes.
• chromatographically-enhancing pore geometry includes the geometry of the pore configuration of the presently-disclosed materials, which has been found to enhance the chromatographic separation ability of the material, e.g., as distinguished from other chromatographic media in the art.
• a geometry can be formed, selected or constructed, and various properties and/or factors can be used to determine whether the chromatographic separations ability of the material has been "enhanced", e.g., as compared to a geometry known or conventionally used in the art. Examples of these factors include high separation efficiency, longer column life and high mass transfer properties (as evidenced by, e.g., reduced band spreading and good peak shape.) These properties can be measured or observed using art-recognized techniques.
• the chromatographically-enhancing pore geometry of the present porous materials is distinguished from the prior art particles by the absence of "ink bottle” or “shell shaped” pore geometry or morphology, both of which are undesirable because they, e.g., reduce mass transfer rates, leading to lower efficiencies.
• Chromatographically-enhancing pore geometry is found in porous materials containing only a small population of micropores. Porous materials with such a low micropore surface area (MSA) give chromatographic enhancements including high separation efficiency and good mass transfer properties (as evidenced by, e.g., reduced band spreading and good peak shape).
• MSA micropore surface area
• Micropore surface area is defined as the surface area in pores with diameters less than or equal to 34A, determined by multipoint nitrogen sorption analysis from the adsorption leg of the isotherm using the BJH method.
• MSA Micropore surface area
• MP A MP A
• the term "functionalizing group” includes organic functional groups which impart a certain chromatographic functionality to a chromatographic stationary phase.
• heterocyclic group includes closed ring structures in which one or more of the atoms in the ring is an element other than carbon, for example, nitrogen, sulfur, or oxygen.
• Heterocyclic groups can be saturated or unsaturated and heterocyclic groups such as pyrrole and furan can have aromatic character. They include fused ring structures such as quinoline and isoquinoline. Other examples of heterocyclic groups include pyridine and purine.
• Heterocyclic groups can also be substituted at one or more constituent atoms with, for example, a halogen, a lower alkyl, a lower alkenyl, a lower alkoxy, a lower alkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, a hydroxyl, -CF3, -CN, or the like.
• Suitable heteroaromatic and heteroalicyclic groups generally will have 1 to 3 separate or fused rings with 3 to about 8 members per ring and one or more N, O or S atoms, e.g.
• metal oxide precursor includes any compound that contains a metal and results in the formation of a metal oxide, e.g., alumina, silica, titanium oxide, zirconium oxide, or cerium oxide.
• the term "monolith” is intended to include a collection of individual particles packed into a bed formation, in which the shape and morphology of the individual particles are maintained.
• the particles are advantageously packed using a material that binds the particles together.
• Any number of binding materials that are well known in the art can be used such as, for example, linear or cross-linked polymers of divinylbenzene, methacrylate, urethanes, alkenes, alkynes, amines, amides, isocyanates, or epoxy groups, as well as condensation reactions of organoalkoxysilanes, tetraalkoxysilanes, polyorganoalkoxysiloxanes,
• the term “monolith” also includes hybrid monoliths made by other methods, such as hybrid monoliths detailed in US Patent No. 7,250,214; hybrid monoliths prepared from the condensation of one or more monomers that contain 0-99 mole percent silica (e.g., Si0 2 ); hybrid monoliths prepared from coalesced porous inorganic/organic particles; hybrid monoliths that have a chromatographically- enhancing pore geometry; hybrid monoliths that do not have a chromatographically-enhancing pore geometry; hybrid monoliths that have ordered pore structure; hybrid monoliths that have non-periodic pore structure; hybrid monoliths that have non-crystalline or amorphous molecular ordering; hybrid monoliths that have crystalline domains or regions; hybrid monoliths with a variety of different macropore and mesopore properties; and hybrid monoliths in a variety of different aspect ratios.
• the term "monolith” also includes hybrid monoliths made by other methods, such as hybrid monoliths detailed in US Patent No.
• nanoparticle is a microscopic particle/grain or microscopic member of a powder/nanopowder with at least one dimension less than about 100 nm, e.g., a diameter or particle thickness of less than about 100 nm (0.1 mm), which may be crystalline or
• Nanoparticles have properties different from, and often superior to those of conventional bulk materials including, for example, greater strength, hardness, ductility, sinterability, and greater reactivity among others.
• Considerable scientific study continues to be devoted to determining the properties of nanomaterials, small amounts of which have been synthesized (mainly as nano-size powders) by a number of processes including colloidal precipitation, mechanical grinding, and gas-phase nucleation and growth. Extensive reviews have documented recent developments in nano-phase materials, and are incorporated herein by reference thereto: Gleiter, H. (1989) "Nano-crystalline materials," Prog. Mater. Sci. 33:223-315 and Siegel, R. W.
• the nanoparticles comprise oxides or nitrides of the following: silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, and mixtures thereof.
• the nanoparticles of the present invention are selected from diamonds, zirconium oxide (amorphous, monoclinic, tetragonal and cubic forms), titanium oxide (amorphous, anatase, brookite and rutile forms), aluminum (amorphous, alpha, and gamma forms), and boronitride (cubic form).
• the nanoparticles of the present invention are selected from nano- diamonds, silicon carbide, titanium dioxide (anatase form), cubic-boronitride, and any combination thereof.
• the nanoparticles may be crystalline or amorphous.
• the nanoparticles are less than or equal to 100 nm in diameter, e.g., less than or equal to 50 nm in diameter, e.g., less than or equal to 20 nm in diameter.
• nanoparticles that are characterized as dispersed within the composites of the invention are intended to describe exogenously added nanoparticles. This is in contrast to nanoparticles, or formations containing significant similarity with putative nanoparticles, that are capable of formation in situ, wherein, for example, macromolecular structures, such as particles, may comprise an aggregation of these endogenously created.
• substantially disordered refers to a lack of pore ordering based on x-ray powder diffraction analysis. Specifically, “substantially disordered” is defined by the lack of a peak at a diffraction angle that corresponds to a d value (or d-spacing) of at least 1 nm in an x- ray diffraction pattern.
• “Surface modifiers” include (typically) organic functional groups which impart a certain chromatographic functionality to a chromatographic stationary phase.
• the porous organic functional groups include (typically) organic functional groups which impart a certain chromatographic functionality to a chromatographic stationary phase.
• inorganic/organic hybrid particles possess both organic groups and silanol groups which may additionally be substituted or derivatized with a surface modifier.
• surface modified is used herein to describe the composite material of the present invention that possess both organic groups and silanol groups which may additionally be substituted or derivatized with a surface modifier.
• Surface modifiers include (typically) organic functional groups which impart a certain chromatographic functionality to a chromatographic stationary phase. Surface modifiers such as disclosed herein are attached to the base material, e.g., via derivatization or coating and later crosslinking, imparting the chemical character of the surface modifier to the base material.
• the organic groups of a hybrid material e.g., particle, react to form an organic covalent bond with a surface modifier.
• the modifiers can form an organic covalent bond to the material's organic group via a number of mechanisms well known in organic and polymer chemistry including but not limited to nucleophilic, electrophilic, cycloaddition, free-radical, carbene, nitrene, and carbocation reactions.
• Organic covalent bonds are defined to involve the formation of a covalent bond between the common elements of organic chemistry including but not limited to hydrogen, boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, and the halogens.
• carbon-silicon and carbon-oxygen-silicon bonds are defined as organic covalent bonds, whereas silicon-oxygen-silicon bonds that are not defined as organic covalent bonds.
• nanoparticle is a microscopic particle/grain or microscopic member of a powder/nanopowder with at least one dimension less than about 100 nm, e.g., a diameter or particle thickness of less than about 100 nm (0.1 ⁇ ), which may be crystalline or
• Nanoparticles have properties different from, and often superior to those of conventional bulk materials including, for example, greater strength, hardness, ductility, sinterability, and greater reactivity among others.
• Considerable scientific study continues to be devoted to determining the properties of nanomaterials, small amounts of which have been synthesized (mainly as nano-size powders) by a number of processes including colloidal precipitation, mechanical grinding, and gas-phase nucleation and growth. Extensive reviews have documented recent developments in nano-phase materials, and are incorporated herein by reference thereto: Gleiter, H. (1989) "Nano-crystalline materials," Prog. Mater. Sci. 33:223-315 and Siegel, R. W.
• the nanoparticles comprise oxides or nitrides of the following: silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, and mixtures thereof.
• the nanoparticles of the present invention are selected from diamonds, zirconium oxide (amorphous, monoclinic, tetragonal and cubic forms), titanium oxide (amorphous, anatase, brookite and rutile forms), aluminum (amorphous, alpha, and gamma forms), and boronitride (cubic form).
• the nanoparticles of the present invention are selected from nano- diamonds, silicon carbide, titanium dioxide (anatase form), cubic-boronitride, and any combination thereof.
• the nanoparticles may be crystalline or amorphous.
• the nanoparticles are less than or equal to 100 ⁇ in diameter, e.g., less than or equal to 50 ⁇ in diameter, e.g., less than or equal to 20 ⁇ in diameter.
• nanoparticles that are characterized as dispersed within the composites of the invention are intended to describe exogenously added nanoparticles. This is in contrast to nanoparticles, or formations containing significant similarity with putative nanoparticles, that are capable of formation in situ, wherein, for example, macromolecular structures, such as particles, may comprise an aggregation of these
• Nanoparticles are of great scientific interest as they are effectively a bridge between bulk materials and atomic or molecular structures.
• a bulk material should have constant physical properties regardless of its size, but at the nano-scale this is often not the case. Size-dependent properties are observed such as quantum confinement in semiconductor particles, surface plasmon resonance in some metal particles and superparamagnetism in magnetic materials. The properties of materials change as their size approaches the nanoscale and as the percentage of atoms at the surface of a material becomes significant. For bulk materials larger than one micrometer the percentage of atoms at the surface is minuscule relative to the total number of atoms of the material. The interesting and sometimes unexpected properties of nanoparticles are partly due to the aspects of the surface of the material dominating the properties in lieu of the bulk properties. In certain embodiments, selection of the nanoparticle affects the selectivity of the chromatographic material. For example, dispersion of Ti0 2 or zirconium oxide could modify the surface charge, surface acidity, and therefore, the chromatographic selectivity.
• composite material and the term “composite” are used interchangeably herein to describe the engineered materials of the invention composed of one or more components described herein in combination with dispersed nanoparticles, wherein each component/nanoparticle remains separate and distinct on a macroscopic level within the finished structure.
• the composite material of the present invention is independent of form, and may be monolithic or particulate in nature.
• the composite materials of the present invention may be nanocomposites, which are known to include, at least, for example, nano/nano- type, intra-type, inter-type, and intra inter-type. (Nanocomposites Science and Technology, edited by P.M. Ajayan, L.S. Schadler, P.V. Braun, Wiley- VCH (Weinheim, Germany), 2003)
• the terms "material having a high thermal conductivity”, “high thermal conductivity core”, and a “high thermal conductivity additive” are defined as a material, core material, or composite additive having a thermal conductivity greater than 20 W/(m K).
• the additive has a thermal conductivity ranges from: about 20 W/(m K) to not more than 3500 W/(m K); about 100 W/(m K) to not more than 3300 W/(m K); and 400 W/(m K) to not more than 3000 W/(m K).
• High thermal conductivity cores or additives can be, for example and without limitation, a 0.1-8 ⁇ core particle, nanoparticle additives, or a metal oxide precursor.
• the high thermal conductivity core or additive includes (but is not limited to) aluminum, copper, gold, and diamonds.
• a "high thermal diffusivity" core or additive is defined as an additive used in a superficially porous materials as having a thermal diffusivity greater than 20 mm 2 /s.
• the core or additive has a thermal diffusivity ranges from: about 20 mm 2 /s to not more than 2000 mm 2 /s; about 100 mm 2 /s to not more than 1600 mm 2 /s; and 150 mm 2 /s to not more than 1400 mm 2 /s.
• This high thermal conductivity core or additive can be a 0.1-8 ⁇ core particle, nanoparticle additives, or a metal oxide precursor.
• the high thermal conductivity core or additive includes (but is not limited to) aluminum, copper, gold, and diamonds.
• a "high thermal conductivity superficially porous material (or particle)" is defined as a material that has improved thermal conductivity or improved thermal diffusivity over a porous silica particle of the same size.
• the higher thermal conductivity superficially porous material is a material that has improved thermal conductivity or thermal diffusivity over a superficially porous silica particle of the same size.
• the higher thermal conductivity superficially porous material is a material that has improved thermal conductivity over a fully porous hybrid particle of the same size. Determination of particle thermal conductivity can be made by the method of Gritti and Guiochon [J. Chromatogr. A, 2010, 1217, 5137) taking into account differences in bulk material properties, pore volume, surface modification type and coverage.
• magnetic material is defined as a material, core material, or composite additive that gas a mass magnetization ( ⁇ , magnetic moment per unit mass, magnetic saturation or saturation magnetization) at room temperature greater than 15 emu/g (A m 2 /kg).
• Magnetic core particles do not include other oxides of iron, including hematite and goethite, that have mass magnetization values less than 10 emu/g. Hematite (0.4 emu/g) is considered antiferromagnetic at room temperature.
• fines refers to undesired materials generated in the processes of the invention that are below the 10 vo% of the target particle size distribution. Fines can be formed from reseeding events or from particle breakage. Resulting fines can be nonporous or fully porous. Often fines are substantially smaller than the 10 vol% of the target particle size distribution. Often fines are ⁇ 1 um in size. Very small fines can cause problems in
• Fines small enough to percolate through the packed bed and outlet frit can result in problems with detectors and can contaminate a product. Problems with detector include clogging flow channels, blocking detector windows, and anomalous detector readings. Such issues can reduce the lifetime of a detector and can require extensive cleaning protocols. Such issues can also impact the precision, accuracy, reliability, reproducibility, and robustness of analytical data generated. Fines can be removed by classification.
• aggregates and agglomerates refer to undesired materials generated in the processes of the invention that are larger than the 90 vol% of the target particle size distribution, aggregates and/or agglomerates can form from imperfections of the core material, improper mixing or dispersion in the process, or excessive forces during workup. Aggregates and agglomerates can impact the efficiency, permeability, reproducibility and robustness of packed beds within chromatographic columns. It is difficult to optimally pack a chromatographic column with materials having an elevated amount of aggregates and agglomerates. Aggregates and agglomerates can break apart within a packed bed structure when exposed to high pressures and shears. This can result in a mechanical instability of the packed bed and the result of a void on the top of the column. This breaking of aggregates and agglomerates can also result in the generation of fines. Aggregates and agglomerates can be removed by classification.
• Hybrid particle technologies are highly desirable for many chromatographic applications due to the increased chemical stability and reduced silanol activity they provide.
• One key advantage of hybrid particles over silica and hybrid coated silica particles in chromatographic applications is their superior column stability when used with alkaline mobile phases (pH 8-12). Silica and hybrid coated silica packing materials have limited lifetimes under these conditions due to the dissolution of the silica and collapse of the packed bed.
• spherical silica or hybrid non-porous cores are prepared following standard protocols.
• a superficially porous layer is formed using two or more of the following; TEOS, a thermally degradable organofunctional silane (e.g., acetoxypropyltrialkoxysilane or bromoethyltrialkoxysilane) along with a more thermally stable hybrid silanes, such as (but not limited to) phenylene bridged silanes.
• TEOS a thermally degradable organofunctional silane
• a more thermally stable hybrid silanes such as (but not limited to) phenylene bridged silanes.
• lower temperature thermal treatment ⁇ 500 °C
• the temperature is determined by TGA experiments performed in air.
• spherical hybrid non-porous cores are prepared following standard protocols.
• a superficially porous layer is prepared using a surfactant or a mixed surfactant approach using one or more silanes that include (but is not limited to) TEOS, a lower temperature degradable organofunctional silane (e.g., acetoxypropyltrialkoxy silane or bromoethyltrialkoxysilane), ethylene bridged alkoxysilanes, or phenylene bridged alkoxysilanes.
• the surfactant is removed using an acid ethanol process (e.g., hydrochloric acid in ethanol).
• the surfactant is removed by thermal treatment ( ⁇ 500 °C) at a temperature that preserves the hybrid group, while removing the surfactant. This temperature is determined by TGA experiments performed in air.
• the surfactant is removed by oxidation (e.g., ozonolysis).
• one or more of the surfactants used in this process are selected from the group of acid labile, base labile, or other labile surfactants. These labile surfactants can be reacted and removed later by selecting the correct chemical conditions (e.g., acid hydrolysis, base hydrolysis, reduction or oxidation, hydrogenation or hydrogenolysis). Additional steps of classification, pore modification, acid treatment and bonding are performed, as detailed above.
• spherical silica or hybrid non-porous cores are prepared following standard protocols. Separately a hybrid sol ( ⁇ 100 nm) solution is prepared using one or more silanes that include (but is not limited to) TEOS, lower temperature degradable organofunctional silane (e.g., acetoxypropyltrialkoxysilane or bromoethyltrialkoxysilane), ethylene bridged alkoxysilanes, or phenylene bridged alkoxysilanes.
• TEOS lower temperature degradable organofunctional silane
• ethylene bridged alkoxysilanes e.g., ethylene bridged alkoxysilanes, or phenylene bridged alkoxysilanes.
• a uniform superficially porous layer is then prepared in a layer-by-layer approach using a suitable positively charged polyelectrolyte.
• Suitable polyelectrolytes include (but is not limited to) linear, branched, and block polymers containing one or more of the following groups; alkyl, cycloalkyl, aryl, ethylene oxide groups along with one or more of the following groups; primary, secondary, tertiary and quaternary amino groups, pyrrolidone, pyridine, and imidazole.
• the polyelectrolyte is removed by thermal treatment ( ⁇ 500 °C) at a temperature that preserves the hybrid group, while removing the polyelectrolyte. This temperature is determined by TGA experiments performed in air. Alternatively the polyelectrolyte is removed by ozonolysis. Additional steps of classification, pore modification, acid treatment and bonding are performed, as detailed herein. Higher thermal conductivity superficially porous particles.
• diamond nanoparticles can be incorporated within non-porous cores (including non-porous silica)
• a diamond core 0.5-3 ⁇
• a non-porous silica or hybrid surface coating may be advantageously used. This surface coating step may be advantageously repeated or performed in a growth-process to achieve the desired thickness. Calcination and surface rehydroxylation may be advantageoulsy used at the end of this step.
• the superficially porous layer may be silica or hybrid, and can be prepared in any of the processes described herein. Additional steps of classification, calcination, pore modification, re- calcination, rehydroxylation and bonding are then performed (as required), as detailed herein.
• Monodisperse non-porous, fully porous and superficially porous particles have been reported.
• the ability to prepare monodisperse particles is a function of the non-porous core as well as the uniformity of the porous layer.
• the materials of the instant invention provide improved permeability as well as improved chemical stability with high pH mobile phases.
• a further improvement in permeability can be achieved if the particle shape is modified.
• a uniform micron-sized doughnut, rod, dumbbell, star, or bent-rod-shaped cores is used in place of a highly spherical core.
• Additional shapes include (but not limited to) spirals, discoidal, concave disks, spools, rings, helix, saddles, cross, cube, derby, helix, cylinders, and tubes.
• dumbbell, doughnut, rod, spiral, and gyroid particles have been reported ⁇ Doshi, N. PNAS, 2009, 106, 51, 21495; Alexander, L. Chem. Commun., 2008, 3507; Naik, S. /. Phys. Chem. C 2007, 111, 11168; Pang, X.
• non-spherical cores are relatively uniform in dimensions, free-flowing, non-porous, and mechanically strong enough for use in HPLC and
• the composition of these cores may be selected from (but is not limited to) silica, metal oxides, diamonds, heavily cross linked polymers, and hybrid materials. Improvements in core uniformity can be achieved through classification. A reduction in porosity can be achieved by pore filling with a similar or different composition (e.g., pore filling a silica material with a crosslinked polymer composition). Improvements in mechanical strength is achieved by increasing crosslinking with the same or different composition (e.g., creating a silica network within a polymer composition), or by calcination. For the latter, higher temperatures (e.g., >800 °C) may be advantageously used.
• higher temperatures e.g., >800 °C
• a non-porous surface coating with a silica, hybrid, or polymeric composition may be advantageously used.
• This surface coating step may need to be repeated or performed in a growth-process to achieve the desired thickness.
• advantageoulsy provides a uniform surface layer. Calcination and surface rehydroxylation may be advantageoudly used at the end of this step.
• a uniform silica or hybrid superficially porous layer may be formed from any one of the processes described above. To ensure the core morphology is not substantially modified, this step advantageously yields a highly uniform porous layer. Additional steps of classification, calcination, pore modification, re-calcination, rehydroxylation and bonding are then performed (as required) as detailed above. These non-spherical superficially porous materials can be packed in chromatographic columns individually or as mixtures with other shapes, or with spherical particles. It is important to optimize column packing conditions for these mixed systems. Considerations of maintaining similar dispersion, bulk density and settling rates between the different materials need to be made. Improved Process to Prepare Superficially Porous Materials.
• redisperse particles there are also many methods available to redisperse particles, including sonication using sonic baths, in-line sonicators, in-tank sonicators, sonic horns, rotor-stator mixers, milling, low shear and high shear mixing (e.g., saw-tooth impellers). Optimization of amplitude, frequency and pulse sequences is used for optimal sonication. Adjusting the conductivity, pH and surfactant mixture can also be used to optimally redisperse particles (through solvent washes, or controlled order of addition of reagents).
• One concern for these redispersion methods is the potential to harm the superficially porous layer. It is expected that elevated shears may result in a fracturing of the porous layer. The resulting material may have bare-spots, or nonuniform porous layers.
• a further concerns is the long reaction times required for an iterative process, such as those described by AMT and the University of Cork. While such materials can be prepared on a laboratory and batch scale, the times required for these processes can exceed those typically used for the synthesis of fully porous particles.
• magnetic capture methods are used to collect magnetic core particles in place of centrifugation or filtration. These methods include in-tank, in-line, or off-line magnetic capture.
• In-tank magnetic capture uses a removable magnetic rod (or alternatively an electromagnet) placed within a removable or permanent glass sleeve or baffle.
• the magnetic rod is placed within the glass sleeve during the time of capture. After the remaining reaction solution is emptied and a new wash or reaction solvent is added, the magnetic rod is removed and bound magnetic core particles are redispersed.
• an external magnet is placed on the side of the reactor allowing magnetic core particles to be captured on the reactor side-wall. After the remaining reaction solution is emptied and a new wash or reaction solvent is added, the external magnet is removed and bound magnetic core particles are redispersed.
• the in-line magnetic capture method involves pumping the reaction solution in a recirculation loop through a collection container.
• This collection container is placed within a magnetic holding block. Magnetic core particles are collected in this container. After the remaining reaction solution is emptied and a new wash or reaction solvent is added, the collection container is removed from the magnetic holding block and the bound magnetic core particles are redispersed as they are pumped back into the reaction vessel.
• this approach has an advantage in that it allows for good control of the surface area exposed to the magnetic field.
• the off-line magnetic capture method is similar to filtration in that the reaction solution is transferred to a secondary vessel.
• a magnetic field is applied to allow for the controlled collection of magnetic core particles.
• Reaction solution or wash solvents are removed by filtration, decanting, or by siphon.
• Magnetic core particles are redispersed in the appropriate solvent and transferred back to the reaction vessel.
• a non-porous magnetic core is used in place of a non-porous silica or hybrid core.
• This magnetic core can contain (but is not limited to) magnetic forms of iron oxides, iron, metals, metal oxides, chromium dioxide, ferrites, or cobalt.
• the magnetic core contains magnetite, maghemite.
• the magnetic core can exist as a pure metal or metal oxide or exist in combination with a second material that includes (but is not limited to) silica, hybrid, polymer, or non-magnetic materials.
• a magnetic core can be formed by incorporating ⁇ 100 nm magnetite or cobalt nanoparticles within non-porous silica or polymer particles.
• the magnetic nanoparticles can be homogeneously dispersed nanoparticles or dispersed clusters of nanoparticles within this material, adsorbed only to the surface, or contained only in the interior of the non -porous core particles.
• 0.3-1.5 ⁇ magnetite or cobalt particles can be used as the non-porous core. Magnetic capture methods are used in this process in place of centrifugation or filtration.
• a non-porous surface coating with a silica, hybrid, or polymeric composition may be advantageously used.
• This surface coating step may be advantageously repeated or performed in a growth-process to achieve the desired thickness. Magnetic capture methods are used in this process in place of centrifugation or filtration. To ensure that the core morphology is not substantially modified, this step advantageously provides a uniform surface layer. Calcination and surface
• rehydroxylation may advantageously used at the end of this step.
• a uniform silica or hybrid superficially porous layer may be formed from any one of the processes described above. To ensure the core morphology is not substantially modified, this step advantageously yield a highly uniform porous layer. Magnetic capture methods are used in this process in place of centrifugation or filtration. Additional steps of classification, calcination, pore modification, re-calcination, rehydroxylation and bonding are then performed (as required) as detailed above.
• a magnetic core particle allows for a unique means to separate the porous layer materials from reseeded particles. This can be utilized in-process or during product workup.
• magnetic core particles as well as magnetic capture methods allows for a unique process of automating the synthesis of superficially porous particles.
• in-tank magnetic capture e.g., using electromagnets
• Automated bottom valves and solvent addition valves are used to fully automate synthesis conditions.
• In-tank or in-line particle size measurements are used to monitor reaction performance and determined reaction completion.
• the invention provides superficially porous materials, particles and/or monoliths comprising a substantially nonporous inorganic/organic core and one or more layers of a porous shell material surrounding the core.
• the superficially porous material of the invention a substantially narrow particle size distribution.
• the ratio of particle sizes is from 1.00-1.55. In specific embodiments, the ratio of particle sizes is from 1.00-1.10 or from 1.05-1.10. In other specific embodiments, the ratio of particle sizes is from 1.10-1.55; from 1.10-1.50; or from 1.30-1.45.
• the superficially porous material of the invention wherein the material has chromatographically enhancing pore geometry. That is, in some embodiments, the superficially porous material of the invention has only a small population of micropores.
• the substantially nonporous core material is silica; silica coated with an inorganic/organic hybrid surrounding materia; a magnetic core material; a magnetic core material coated with silica; a high thermal conductivity core material; a high thermal conductivity core material coated with silica; a composite material; an inorganic/organic hybrid surrounding material; a composite material coated with silica; a magnetic core material coated with an inorganic/organic hybrid surrounding material; or a high thermal conductivity core material coated with an inorganic/organic hybrid surrounding material.
• the core materials are composite materials.
• Composite materials describe the engineered materials of the invention composed of one or more components described herein in combination with dispersed nanoparticles, wherein each component/nanoparticle remains separate and distinct on a macroscopic level within the finished structure.
• the composite material of the present invention is independent of form, and may be monolithic or particulate in nature.
• the short-hand convention used herein to describe a composite material containing a dispersed nanoparticle, Np/(A) w (B) x (C) y may be understood as follows: the symbolic representation to the left of the slash mark represents the dispersed nanoparticle, and the symbolic representations to the right of the slash mark represent the components that comprise the material that the nanoparticle (noted on the left of the slash mark) is dispersed within.
• the composite materials of the present invention may be nanocomposites, which are known to include, at least, for example, nano/nano-type, intra-type, inter-type, and intra/inter-type. (Nanocomposites Science and Technology, edited by P.M.
• nanoparticle is a microscopic particle/grain or microscopic member of a powder/nanopowder with at least one dimension less than about 100 nm, e.g., a diameter or particle thickness of less than about 100 nm (0.1 ⁇ ), which may be crystalline or noncrystalline. Nanoparticles have properties different from, and often superior to those of conventional bulk materials including, for example, greater strength, hardness, ductility, sinterability, and greater reactivity among others.
• the nanoparticles comprise oxides or nitrides of the following: silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, and mixtures thereof.
• the nanoparticles of the present invention are selected from diamonds, zirconium oxide (amorphous, monoclinic, tetragonal and cubic forms), titanium oxide (amorphous, anatase, brookite and rutile forms), aluminum (amorphous, alpha, and gamma forms), and boronitride (cubic form).
• the nanoparticles of the present invention are selected from nano-diamonds, silicon carbide, titanium dioxide (anatase form), cubic-boronitride, and any combination thereof. Moreover, in particular embodiments, the nanoparticles may be crystalline or amorphous. In particular embodiments, the nanoparticles are less than or equal to 100 ⁇ in diameter, e.g., less than or equal to 50 ⁇ in diameter, e.g., less than or equal to 20 ⁇ in diameter.
• nanoparticles that are characterized as dispersed within the composites of the invention are intended to describe exogenously added nanoparticles. This is in contrast to nanoparticles, or formations containing significant similarity with putative nanoparticles, that are capable of formation in situ, wherein, for example, macromolecular structures, such as particles, may comprise an aggregation of these
• Nanoparticles are of great scientific interest as they are effectively a bridge between bulk materials and atomic or molecular structures.
• a bulk material should have constant physical properties regardless of its size, but at the nano-scale this is often not the case. Size-dependent properties are observed such as quantum confinement in semiconductor particles, surface plasmon resonance in some metal particles and superparamagnetism in magnetic materials.
• the composite materials include magnetic materials, materials having a high thermal conductivity, or mixtures thereof.
• the cores themselves are magnetic materials, materials having a high thermal conductivity or mixtures thereof.
• Materials having a high thermal conductivity, high thermal conductivity cores or a high thermal conductivity additives are defined as materials having a thermal conductivity greater than 20 W/(m K).
• the additive has a thermal conductivity ranges from: about 20 W/(m K) to not more than 3500 W/(m K); about 100 W/(m K) to not more than 3300 W/(m K); and 400 W/(m K) to not more than 3000 W/(m K).
• This high thermal conductivity additive can be a 0.1 -8 ⁇ core particle, nanoparticle additives, or a metal oxide precursor.
• the high thermal conductivity additive includes (but is not limited to) aluminum, copper, gold, and diamonds.
• a high thermal diffusivity additive is defined as an additive used in a superficially porous particle having a thermal diffusivity greater than 20 mm 2 /s.
• the additive has a thermal diffusivity ranges from: about 20 mm 2 /s to not more than 2000 mm 2 /s; about 100 mm 2 /s to not more than 1600 mm 2 /s; and 150 mm 2 /s to not more than 1400 mm 2 /s.
• This high thermal conductivity additive can be a 0.1-8 ⁇ core particle, nanoparticle additives, or a metal oxide precursor.
• the high thermal conductivity additive includes (but is not limited to) aluminum, copper, gold, and diamonds.
• a magnetic material include materials that have a mass magnetization ( ⁇ , magnetic moment per unit mass, magnetic saturation or saturation magnetization) at room temperature greater than 15 emu/g (A m 2 /kg).
• Magnetic core particles do not include other oxides of iron, including hematite and goethite, that have mass magnetization values less than 10 emu/g. Hematite (0.4 emu/g) is considered antiferromagnetic at room temperature.
• the cores are spherical.
• the spherical core has a non-crystalline or amorphous molecular ordering.
• the spherical core has a non-periodic pore structure.
• the core has an average size of about 0.1 ⁇ to about 300 ⁇ . In a further embodiment, the core has an average size of about 0.1 ⁇ to about 30 ⁇ . In a further embodiment, the core has an average size of about 0.5 ⁇ to about 30 ⁇ . In a further embodiment, the core has an average size of about 0.9 ⁇ to about 10 ⁇ . In a further embodiment, the core has an average size of about 1.0 ⁇ to about 3.0 ⁇ .
• the core material of the invention a substantially narrow particle size distribution.
• the 90 /i 0 ratio of particle sizes is from 1.00-1.55.
• the 90 /i 0 ratio of particle sizes is from 1.00-1.10 or from 1.05-1.10.
• the 90 /i 0 ratio of particle sizes is from 1.10-1.55; from 1.10-1.50; or from 1.30-1.45.
• the core is hydrolytically stable at a pH of about 1 to about 14. In one embodiment, the core is hydrolytically stable at a pH of about 10 to about 14. In another embodiment, the core is hydrolytically stable at a pH of about 1 to about 5.
• the materials of the invention have one or more layers of a porous shell material applied to the substantially non-porous core.
• one or more layers of porous shell material are a porous inorganic/organic hybrid material; a porous silica or a porous composite material.
• the materials of the invention have a rough surface. In still other aspects, the materials of the invention have a smooth surface. As used herein,
• each porous layer is independently from 0.02 ⁇ to 5 ⁇ . in thickness as measured perpendicular to the surface of the nonporous core.
• each porous layer is independently from 0.06 ⁇ to 1 ⁇ . in thickness as measured perpendicular to the surface of the nonporous core.
• each porous layer is independently from 0.20 ⁇ to 0.70 ⁇ . in thickness as measured perpendicular to the surface of the nonporous core.
• the materials of the invention have between 1 and 15 layers of porous shell material. In other embodiments between 2 and 5 layers of porous shell material. In still others 1 or 2 layers of porous shell materials.
• the porous hybrid layer material or shell material which may be layered onto the core may be independently derived from
• partially condensed polymeric organofunctional metal precursors a mixture of two or more polymeric organofunctional metal precursors, or a mixture of one or more polymeric organofunctional metal precursors with a polymeric metal oxide precursors on the surface of the core.
• the inorganic portion of the surrounding material is independently selected from the group consisting of alumina, silica, titania, cerium oxide, or zirconium oxides, and ceramic materials.
• the hybrid layer material may independently derived from condensation of one or more organofunctional silanes and/or tetraalkoxysilane on the surface of the core, or
• organofunctional silane a mixture of two or more organofunctional silanes, or a mixture of one or more organofunctional silanes with a tetraalkoxysilane (i.e., tetraethoxysilane, tetramethoxysilane) on the surface of the core.
• a tetraalkoxysilane i.e., tetraethoxysilane, tetramethoxysilane
• the hybrid layer material may independently comprise from about 0- 100 mol% hybrid material.
• the inorganic portion of the surrounding material may independently be alumina, silica, titanium oxide, cerium oxide, zirconium oxide or ceramic materials or a mixture thereof.
• the inorganic portion of the hybrid layer material may independently be present in an amount ranging from about 0 molar % to not more than about 25 molar %, wherein the pores of the surrounding material are substantially disordered.
• the inorganic portion of the surrounding material may independently be present in an amount ranging from about 25 molar % to not more than about 50 molar %, wherein the pores of the surrounding material are substantially disordered, and wherein the hybrid layer material may or may not independently possesses a chromatographically enhancing pore geometry (CEPG).
• CEPG chromatographically enhancing pore geometry
• the inorganic portion of the hybrid layer material may independently be present in an amount ranging from about 50 molar % to not more than about 75 molar %, wherein the pores of the hybrid layer material are substantially disordered, and wherein the hybrid layer material independently possesses a chromatographically enhancing pore geometry (CEPG).
• CEPG chromatographically enhancing pore geometry
• the inorganic portion of the hybrid layer material may independently be present in an amount ranging from about 75 molar % to not more than about 100 molar %, wherein the pores of the hybrid layer material are substantially disordered, and wherein the hybrid layer material may or may not independently possesses a
• CEPG chromatographically enhancing pore geometry
• the inorganic portion of the hybrid layer material may independently be present in an amount ranging from about 0 molar % to not more than about 100 molar %; specifically, 0%-10%, 0%-5%, 0%-4%, 0%-3%, 0%-2%, 0%-l %, 1 %-10%, 1 %- 5%, l %-4%, l %-3%, l %-2%, 5%-100%, 10%-100%, 15%-100%, 20%-100%, 25%-100%, 30%-100%, 35%- 100%, 40%-100%, 45%-100%, 55%-100%, 60%-100%, 65%-100%, 70%- 100%, 75%-100%, 80%-100%, 81 %-100%, 82%-100%, 83%-100%, 84%- 100%, 85%-100%, 86%-100%, 87%- 100%, 88%-100%, 89%-100%, 90%-100%, 91 %-100%, 92%-100%, 93%- 100%, 94%-100%, 95%
• the hybrid layer material may comprise a material of formula I:
• R and R are each independently Ci-Ci 8 alkoxy, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, C 3 -Ci 8 cycloalkyl, Ci-Ci 8 heterocycloalkyl, C 5 -Ci 8 aryl, C 5 -Ci 8 aryloxy, or C 1 -C18 heteroaryl;
• R 2 is C 1 -C18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C C 18 heterocycloalkyl, Cs-Ci 8 aryl, Ci-Ci 8 heteroaryl; or absent; wherein each R 2 is attached to two or more silicon atoms;
• p and q are each independently 0.0 to 3.0;
• t is 0.5, 1.0, or 1.5;
• d is 0 to about 30;
• n is an integer from 1-20; wherein R, R 1 and R 2 are optionally substituted;
• the hybrid layer material may comprise a material of formula II :
• R and R are each independently Ci-Ci 8 alkoxy, Ci-Ci 8 alkyl, Ci-Ci 8 alkyl, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, C 3 -Ci 8 cycloalkyl, Ci-Ci 8 heterocycloalkyl, Cs-Ci 8 aryl, Cs-Ci 8 aryloxy, or C 1 -C18 heteroaryl;
• d is 0 to about 30;
• the hybrid layer material may comprise a material of formula III:
• R 1 is C 1 -C18 alkoxy, C C 18 alkyl, C C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, Ci-Ci 8 heterocycloalkyl, Cs-Ci 8 aryl, Cs-Ci 8 aryloxy, or Ci-Ci 8 heteroaryl;
• R 2 is C 1 -C18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 3 -C 18 cycloalkyl, C C 18 heterocycloalkyl, Cs-Ci 8 aryl, Ci-Cis heteroaryl; or absent; wherein each R 2 is attached to two or more silicon atoms;
• d is 0 to about 30;
• the hybrid layer material may comprise a material of formula IV:
• repeat units A, B, and C may be random, block, or a combination of random and block;
• A is an organic repeat unit which is covalently bonded to one or more repeat units A or
• B is an organosiloxane repeat unit which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;
• C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond;
• z 0, then 0.002 ⁇ x/y ⁇ 210, and when z ⁇ 0, then 0.0003 ⁇ y/z ⁇ 500 and 0.002 ⁇ x/(y+z) ⁇ 210.
• the hybrid layer material may comprise a material of formula
• repeat units A, B, B*, and C may be random, block, or a combination of random and block;
• A is an organic repeat unit which is covalently bonded to one or more repeat units A or
• B is an organosiloxane repeat units which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;
• B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization;
• C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond;
• z 0, then 0.002 ⁇ x/(y+y*) ⁇ 210, and when z ⁇ 0, then 0.0003 ⁇ (y+y*)/z ⁇ 500 and 0.002 ⁇ x/(y+y*+z) ⁇ 210.
• R 2 in the formulas presented above may be present or absent.
• R 1 in the formulas presented above is Ci-Ci 8 alkyl group substituted by hydroxyl. In still other aspects, R 1 in the formulas presented above is hydroxypropyl. In still other aspects, the hydroxy substituted alkyl group is further functionalized by an isocyanate.
• the isocyanate is octadecyl isocyanate, dodecyl isocyanate, pentafluorophenyl isocyanate, 4-cyanophenyl isocyanate, 3-cyanophenyl isocyanate, 2-cyanophenyl isocyanate, phenyl isocyate, benzyl isocyanate, phenethyl isocyanate or diphenylethyl isocyante.
• the organosiloxane is, without limitation, phenyltriethoxysilane; phenyltrimethoxysilane; phenylethyltriethoxysilane; phenylethyltrimethoxysilane;
• ethyltriethoxysilane ethyl trimethoxysilane; methyltriethoxysilane; methyltrimethoxysilane diethyldiethoxysilane; diethyldimethoxysilane l,4-bis(triethoxysilyl)benzene; 1,4- bis(trimethoxysilyl)benzene; 1 ,3-bis(triethoxysilyl)benzene; 1 ,3-bis(trimethoxysilyl)benzene; l,8-bis(triethoxysilyl)octane; l,8-bis(trimethoxysilyl)octane; l,2-bis(trimethoxysilyl)ethane; 1,2- bis(methyldiethoxysilyl)ethane; 1 ,2-bis(methyldimethoxysilyl)ethane; vinyl trie thoxysilane; vinyltrimethoxysilane;
• chloropropyltriethoxysilane chloropropyltrimethoxysilane; octadecyltrimethoxysilane;
• octadecyltriethoxysilane octyltrimethoxysilane; octyltriethoxysilane; 3,3.3- trifluoropropyltrimethoxysilane; 3 ,3.3 -trifluoropropyltriethoxysilane; 3- cyanobutyltriethoxysilane; and 3-cyanobutyltrimethoxysilane alone or in a mixture with tetraethoxysilane or tetramethoxysilane.
• the organosiloxane is, without limitation, a substituted benzene, including (but not limited to) l,4-bis(triethoxysilyl)benzene, l,4-bis(trimethoxysilyl)benzene,
• the invention provides materials as described herein wherein the hybrid layer material further comprises a nanoparticle or a mixture of more than one nanoparticles dispersed within the core.
• the nanoparticle is present in ⁇ 20% by weight of the nanocomposite, ⁇ 10% by weight of the nanocomposite, or ⁇ 5% by weight of the nanocomposite.
• the nanoparticle is crystalline or amorphous and may be silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, oxides thereof, or a nitride thereof.
• the nanoparticle is a substance which comprises one or more moieties selected from the group consisting of nano- diamonds, silicon carbide, titanium dioxide, cubic -boronitride.
• the nanoparticles may be less than or equal to 200 ⁇ in diameter, less than or equal to 100 ⁇ in diameter, less than or equal to 50 ⁇ in diameter, or less than or equal to 20 ⁇ in diameter.
• the porous shell layer materials are porous silica. Porous Composites.
• the porous shell layer materials are composite materials.
• Composite materials describe the engineered materials of the invention composed of one or more components described herein in combination with dispersed nanoparticles, wherein each component/nanoparticle remains separate and distinct on a macroscopic level within the finished structure.
• the composite material of the present invention is independent of form, and may be monolithic or particulate in nature.
• the short-hand convention used herein to describe a composite material containing a dispersed nanoparticle, Np/(A) w (B) x (C) y may be understood as follows: the symbolic representation to the left of the slash mark represents the dispersed nanoparticle, and the symbolic representations to the right of the slash mark represent the components that comprise the material that the nanoparticle (noted on the left of the slash mark) is dispersed within.
• the composite materials of the present invention may be nanocomposites, which are known to include, at least, for example, nano/nano-type, intra-type, inter-type, and intra/inter-type. (Nanocomposites Science and Technology, edited by P.M.
• nanoparticle is a microscopic particle/grain or microscopic member of a powder/nanopowder with at least one dimension less than about 100 nm, e.g., a diameter or particle thickness of less than about 100 nm (0.1 ⁇ ), which may be crystalline or noncrystalline.
• Nanoparticles have properties different from, and often superior to those of conventional bulk materials including, for example, greater strength, hardness, ductility, sinterability, and greater reactivity among others.
• Considerable scientific study continues to be devoted to determining the properties of nanomaterials, small amounts of which have been synthesized (mainly as nano-size powders) by a number of processes including colloidal precipitation, mechanical grinding, and gas-phase nucleation and growth. Extensive reviews have documented recent developments in nano-phase materials, and are incorporated herein by reference thereto: Gleiter, H. (1989) “Nano-crystalline materials,” Prog. Mater. Sci. 33:223-315 and Siegel, R. W. (1993) "Synthesis and properties of nano-phase materials,” Mater.
• the nanoparticles comprise oxides or nitrides of the following: silicon carbide, aluminum, diamond, cerium, carbon black, carbon nanotubes, zirconium, barium, cerium, cobalt, copper, europium, gadolinium, iron, nickel, samarium, silicon, silver, titanium, zinc, boron, and mixtures thereof.
• the nanoparticles of the present invention are selected from diamonds, zirconium oxide (amorphous, monoclinic, tetragonal and cubic forms), titanium oxide (amorphous, anatase, brookite and rutile forms), aluminum (amorphous, alpha, and gamma forms), and boronitride (cubic form).
• zirconium oxide amorphous, monoclinic, tetragonal and cubic forms
• titanium oxide amorphous, anatase, brookite and rutile forms
• aluminum amorphous, alpha, and gamma forms
• boronitride cubic form
• the nanoparticles of the present invention are selected from nano-diamonds, silicon carbide, titanium dioxide (anatase form), cubic-boronitride, and any combination thereof. Moreover, in particular embodiments, the nanoparticles may be crystalline or amorphous. In particular embodiments, the nanoparticles are less than or equal to 100 ⁇ in diameter, e.g., less than or equal to 50 ⁇ in diameter, e.g., less than or equal to 20 ⁇ in diameter.
• nanoparticles that are characterized as dispersed within the composites of the invention are intended to describe exogenously added nanoparticles. This is in contrast to nanoparticles, or formations containing significant similarity with putative nanoparticles, that are capable of formation in situ, wherein, for example, macromolecular structures, such as particles, may comprise an aggregation of these
• Nanoparticles are of great scientific interest as they are effectively a bridge between bulk materials and atomic or molecular structures.
• a bulk material should have constant physical properties regardless of its size, but at the nano-scale this is often not the case. Size-dependent properties are observed such as quantum confinement in semiconductor particles, surface plasmon resonance in some metal particles and superparamagnetism in magnetic materials.
• the composite materials include magnetic materials, materials having a high thermal conductivity, or mixtures thereof.
• Materials having a high thermal conductivity, high thermal conductivity cores or a high thermal conductivity additive is defined as a material, core or additive used in a superficially porous particle having a thermal conductivity greater than 20 W/(m K).
• the core or additive has a thermal conductivity ranges from: about 20 W/(m K) to not more than 3500 W/(m-K); about 100 W/(m-K) to not more than 3300 W/(m-K); and 400 W/(m-K) to not more than 3000 W/(m K).
• This high thermal conductivity core or additive can be a 0.1 -8 ⁇ core particle, nanoparticle additives, or a metal oxide precursor.
• the high thermal conductivity core or additive includes (but is not limited to) aluminum, copper, gold, and diamonds.
• a high thermal diffusivity additive is defined as an additive used in a superficially porous particle having a thermal diffusivity greater than 20 mm 2 /s.
• the additive has a thermal diffusivity ranges from: about 20 mm 2 /s to not more than 2000 mm 2 /s; about 100 mm 2 /s to not more than 1600 mm 2 /s; and 150 mm 2 /s to not more than 1400 mm 2 /s.
• This high thermal conductivity additive can be a 0.1-8 ⁇ core particle, nanoparticle additives, or a metal oxide precursor.
• the high thermal conductivity additive includes (but is not limited to) aluminum, copper, gold, and diamonds.
• a magnetic material include materials that have a mass magnetization ( ⁇ , magnetic moment per unit mass, magnetic saturation or saturation magnetization) at room temperature greater than 15 emu/g (A m 2 /kg).
• Magnetic core particles do not include other oxides of iron, including hematite and goethite, that have mass magnetization values less than 10 emu/g. Hematite (0.4 emu/g) is considered antiferromagnetic at room temperature.
• the superficially porous materials of the invention utilize core materials having an increased hybrid content near the surface of the core.
• the superfiicially porous material of the invention utilize core materials having a decreased hybrid content near the surface of the core.
• such increase or decrease generally occurs within 1-200 nm of the surface of the core; alternatively within 5-60 nm of the surface of the core.
• the superficially porous materials of the invention include superficially porous materials having an increased hybrid content near the surface of the core.
• the superfiicially porous material of the invention include superficially porous materials having a decreased hybrid content near the surface of the core.
• such increase or decrease generally occurs within 1-200 nm of the surface of the superficially porous material; alternatively within 5-60 nm of the surface of the superficially porous material.
• the superficially porous material of the invention has specific core morphology.
• such core morphology is produced by using cores having the defined shape.
• the core morphology refers to the specific defined shape of the product material of the invention.
• the cores or the product material has a highly spherical, rod shaped, bent-rod shaped, toroid shaped or dumbbell shaped core morphology. In certain other embodiments, the cores or the product material has a mixture of highly spherical, rod shaped, bent-rod shaped, toroid shaped or dumbbell shaped core morphologies.
• the superficially porous material of the invention have significantly higher thermal conductivity than fully porous silica particles of the same size.
• the superficially porous material of the invention have significantly higher thermal conductivity than superficially porous silica particles of the same size. Determination of particle thermal conductivity can be made by the method of Gritti and Guiochon [/. Chromatogr. A, 2010, 1217, 5137) taking into account differences in bulk material properties, pore volume, surface modification type and coverage.
• the superficially porous material of the invention have significantly improved chemical stability when exposed to high pH mobile phases unbonded, fully porous silica particles of the same size. In certain embodiments, the superficially porous material of the invention have significantly improved chemical stability when exposed to high pH mobile phases unbonded, superficially porous silica particles of the same size.
• the superficially porous material of the invention are capable of forming a packed beds with improved permeability as compared to fully porous silica particles of the same size.
• the superficially porous material of the invention are capable of forming a packed beds with improved permeability as compared to superficially porous silica particles of the same size.
• Improved permeability for a give particle size is observed as a decrease in column backpressure. Determination of permeability of packed beds can be made by inverse size exclusion chromatography.
• the superficially porous materials (which are particles) have an average particle size of the material is between 0.8-3.0 ⁇ . Specifically, the average particle size of the material may be between 1.1-2.9 ⁇ ⁇ between 1.3-2.7 ⁇ .
• the superficially porous materials have pores which have an average diameter of about 25-600 A; about 60-350 A; about 80-300 A; or about 90-150 A.
• the superficially porous materials have an average pore volume of about 0.11-0.50 cm 3 /g; about 0.09-0.45 cm 3 /g; or about 0.17-0.30 cm 3 /g.
• the superficially porous materials have a pore surface area between about 10 m 2 /g and 400m 2 /g.
• the materials of the invention may further be surface modified.
• the materials have been surface modified by coating with a polymer.
• R' is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec -butyl, pentyl, isopentyl, hexyl and cyclohexyl.
• R' is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, an alkyl or aryl group containing an embedded polar functionality and a chiral moiety.
• R' is selected from the group consisting of aromatic, phenylalkyl, fluoroaromatic, phenylhexyl,
• R" is a Cl - C30 alkyl group. In a further embodiment, R" comprises a chiral moiety. In another further embodiment, R" is a Cl - C20 alkyl group.
• the surface modifier comprises an embedded polar functionality.
• embedded polar functionality includes carbonate, amide, urea, ether, thioether, sulfinyl, sulfoxide, sulfonyl, thiourea, thiocarbonate,
• such embedded polar functionality includes carbamate functionalities such as disclosed in U. S. Patent No. 5,374,755, and chiral moieties.
• Such groups include those of the general formula
• cyanoalkyl t-butyl, butyl, octyl, dodecyl, tetradecyl, octadecyl, or benzyl.
• octyl dodecyl, or octadecyl.
• the surface modifier is selected from the group consisting of phenylhexyltrichlorosilane, pentafluorophenylpropyltrichlorosilane, octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane and octadecyldimethylchlorosilane.
• the surface modifier is selected from the group consisting of octyltrichlorosilane and octadecyltrichlorosilane.
• the surface modifier is selected from the group consisting of an isocyanate or ⁇ , -carbonyldiimidazole (particularly when the hybrid group contains a (CH 2 ) 3 0H group).
• the material has been surface modified by a combination of organic group and silanol group modification.
• the material has been surface modified by a combination of organic group modification and coating with a polymer.
• the organic group comprises a chiral moiety.
• the material has been surface modified by a combination of silanol group modification and coating with a polymer.
• the material has been surface modified via formation of an organic covalent bond between the particle' s organic group and the modifying reagent.
• the material has been surface modified by a combination of organic group modification, silanol group modification and coating with a polymer.
• the material has been surface modified by silanol group modification.
• the invention provides a method for preparing a superficially porous material comprising:
• the method further provides the step of :
• the approaches described herein allows for the synthesis of narrow particle size distribution fully porous, spherical particles as well as narrow particle size distribution superficially porous (defined as a porous shell layer on a nonporous core particle) particles having a chromatographically enhanced pore geometry.
• the processes involves the condensation of a tetraalkoxysilane (e.g., tetraethoxysilane or tetramethoxysilane) alone or co- condensed with a second organosilane through modification of a traditional Stober-growth process. Listed below are non-limiting descriptions of this process.
• Step 1) Condensation of a tetraalkoxysilane with or without (R 1 ) a (R 2 ) b (R 3 ) c Si(OR 4 ) ⁇ j to form seed particles (0.2-10 ⁇ ) in the presence or absence of surfactants or pore structuring agents (including pore expanding molecules and polymers).
• Step 2 Grow seed particles by condensation of a tetraalkoxysilane with or without
• Step 5 Produce a porous silica particle by removal of organic group and or surfactants by thermal treatment.
• Step 6 Pore structure modification using fluorine containing chemical techniques, including ammonium bifluoride and hydrofluoric acid.
• Step 7) Pore structure modification by hydrothermal processing in the presence or absence of surfactants or pore structuring agents (including pore expanding molecules and polymers).
• Step 8) Improve particle size distribution through particle classification techniques.
• Step 9) Use of elevated temperature treatment (>600°C) to improve particle mechanical stability.
• Step 10 Prepare the particle surface for modification by acid treatment (e.g., hydrochloric acid or hydrofluoric acid).
• acid treatment e.g., hydrochloric acid or hydrofluoric acid.
• Step 1) Condensation of a tetraalkoxysilane with or without (R 1 ) a (R 2 ) b (R 3 ) c Si(OR 4 ) d to form seed particles (0.2-10 ⁇ ) in the presence or absence of surfactants or pore structuring agents.
• Step 2) Grow seed particles by condensation of a tetraalkoxysilane with or without
• Step 3 Further grow particles by co-condensation of a tetraalkoxysilane with
• Step 5 Produce a porous silica particle by removal of organic group and/or surfactants by thermal treatment or extraction techniques.
• Step 6 Pore structure modification using fluorine containing chemical techniques, including ammonium bifluoride and hydrofluoric acid.
• Step 7) Pore structure modification by pseudomorphic transformation in the presence of surfactants and/or pore structuring agents (including pore expanding molecules and polymers).
• Step 8) Surfactant removal by extraction techniques or by calcination.
• Step 9) Pore structure modification by hydrothermal processing in the presence or absence of surfactants or pore structuring agents (including pore expanding molecules and polymers). Step 10) Improve particle size distribution through particle classification techniques
• Step 11 Use of elevated temperature treatment (>600°C) to improve particle mechanical stability.
• Step 12 Prepare the particle surface for modification by acid treatment (e.g., hydrochloric acid or hydrofluoric acid).
• acid treatment e.g., hydrochloric acid or hydrofluoric acid.
• Step 1) Condensation of Si(OCH 2 CH 3 ) 4 to form seed particles (0.2-2 ⁇ )
• Step 2 Grow seed particles by condensation of Si(OCH 2 CH 3 ) 4 to form a larger core particle (0.3-7 ⁇ ).
• R octyl or octadecyl and R' is methyl or ethyl.
• Step 4) Improve particle size distribution through particle classification techniques
• Step 5 Produce a porous silica particle by removal of organic group by thermal treatment (500-
• Step 6 Pore structure modification using ammonium bifluoride (4-20 hours, 25-60°C).
• Step 7) Pore structure modification by hydrothermal processing (7-20 hours, pH 5-7, 90-150°C).
• Step 8) Improve particle size distribution through particle classification techniques
• Step 9) Use of elevated temperature treatment (800-1, 000 °C) to improve particle mechanical stability.
• Step 10 Prepare the particle surface for modification using hydrofluoric acid treatment.
• Step 11 Chemical modification of the particle surface using chlorosilanes coupling and endcapping protocols.
• Step 1) ⁇ 10 ⁇ particles (e.g., diamonds, zirconia, titania, iron oxides, cerium, cobalt, cobalt oxides, carbon, silica, silica carbide) are surface activated through treatment with acid, base, chemical reduction, chemical oxidation, or through attachment of a surface modifying group (e.g., adsorption of an amine, surfactant, silane bond).
• a surface modifying group e.g., adsorption of an amine, surfactant, silane bond.
• Step 2 Particles are grown by condensation of a tetraalkoxysilane with or without
• Step 3 Particle are further grown by co-condensation of a tetraalkoxysilane with
• Step 4) Improve particle size distribution through particle classification techniques
• Step 5 Produce a porous silica particle by removal of organic group and/or surfactants by thermal treatment or extraction techniques.
• Step 6 Pore structure modification using fluorine containing chemical techniques, including ammonium bifluoride and hydrofluoric acid.
• Step 7) Pore structure modification by pseudomorphic transformation in the presence of surfactants and/or pore structuring agents (including pore expanding molecules and polymers).
• Step 8) Surfactant removal by extraction techniques or by calcination.
• Step 9) Pore structure modification by hydrothermal processing in the presence or absence of surfactants or pore structuring agents (including pore expanding molecules and polymers). Step 10) Improve particle size distribution through particle classification techniques
• Step 11 Use of elevated temperature treatment (>600°C) to improve particle mechanical stability.
• Step 12 Prepare the particle surface for modification by acid treatment (e.g., hydrochloric acid or hydrofluoric acid).
• acid treatment e.g., hydrochloric acid or hydrofluoric acid.
• Method D may be useful for preparing superficially porous magnetic particles.
• the invention provides a method for preparing a superficially porous material comprising:
• the method for preparing a superficially porous material further comprises the step of :
• each layer of porous shell material wherein each layer is independently selected from is a porous inorganic/organic hybrid material, a porous silica, a porous composite material or mixtures thereof.
• each layer of porous shell material is applied using sols, a polyelectrolyte or a chemically degradable polymer, wherein:
• the sols are inorganic sols, hybrid sols, nanoparticles, or mixtures thereof; and b) the polyelectrolyte or chemically degradable polymer is removed from the material using chemical extraction, degradation, or thermal treatment at temperatures less than 500°C, or combinations thereof.
• each layer of porous shell material is applied by formation through an electrostatic or acid/base interaction of an ionizable group comprising the steps of:
• the prebonding of the substantially nonporous core or sols includes washing with and acid or base, or a charged polyelectrolyte. In other embodiments, the prebonding of the substantially nonporous core or sols includes chemical transformation of an accessible hybrid organic group.
• the accessible hybrid organic group is an aromatic group that can undergo sulfonation, nitration, amination, or chloromethylation followed by oxidation or nucleophillic displacement with amine containing groups to form ionizable groups.
• the accessible hybrid organic group is an alkene group that can undergo oxidation, cross-metathesis, or polymerization to form ionizable groups.
• the accessible hybrid organic group is an thiol group that can undergo oxidation, radical addition, nucleophillic displacement, or polymerization to form ionizable groups.
• the prebonding of the substantially nonporous core or sols includes bonding with an alkoxysilane that has an ionizable group of equation 1,
• x is 0-3; advantageously 0;
• Y represents chlorine, dimethylamino, triflate, methoxy, ethoxy, or a longer chain alkoxy group
• R represent a basic group, including (but not limited to) -NH 2 , -N(R')H, -N(R') 2 , -N(R' )3 + , -NH(CH 2 ) m NH 2, -NH(CH 2 ) m N(R')H -NH(CH 2 ) m N(R') 2, -NH(CH 2 ) m N(R') 3 + , Pyridyl, imidizoyl, polyamine.
• R' independently represents an alkyl, branched alkyl, aryl, or cycloalkyl group
• n 2-6.
• the prebonding of the substantially nonporous core or sols includes bonding with an alkoxysilane that has an ionizable group of equation 2,
• x is 0-3; advantageously 0;
• Y represents chlorine, dimethylamino, triflate, methoxy, ethoxy, or a longer chain alkoxy group
• A represent an acidic group, including (but not limited to) a sulfonic acid, carboxylic acid, phosphoric acid, boronic acid, arylsulfonic acid, arylcarboxylic acid, arylphosphonic acid, and arylboronic acid.
• R' independently represents an alkyl, branched alkyl, aryl, or cycloalkyl group.
• each layer of porous shell material is applied using a polyelectrolyte or a chemically degradable polymer.
• the polyelectrolyte or a chemically degradable is removed from the material by chemical extraction, degradation, or thermal treatment at temperatures less than 500°C, or combinations thereof.
• each layer of porous shell material is applied using alkoxysilanes, organoalkoxysilanes, nanoparticles, polyorganoalkoxysiloxanes, or combinations thereof, comprising the steps of:
• the alkoxysilanes, organoalkoxysilanes, nanoparticles, polyorganoalkoxysiloxanes, or combinations thereof are condensed on the substantially nonporous core in a solution comprising ethanol, water, ammonium hydroxide, an ionic surfactant; and an non-ionic surfactant.
• the ionic surfactant is Cio-C 3 oN(R) 3 + X " , where R is methyl, ethyl, propyl, alkyl, fluoroalkyl; X is a halogen, hydroxide, or of the form R'S0 3 " or R'C0 2 " where R' is methyl, ethyl, butyl, propyl, isopropyl, tert-butyl, aryl, tolyl, a haloalkyl or a fluoroalkyl group.
• the ionic surfactant is octadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide,
• the concentration of ionic surfactant is maintained in the reaction solution between 5-17 mM; or in certain embodiments between 8-14 mM.
• the non-ionic surfactant is a diblock or triblock copolymer.
• the copolymer is (PEO)x(PPO)y(PEO)x,
• PEO is a polyethylene oxide repeat unit
• PPO is a polypropylene oxide repeat unit
• x is an integer between 5-106,
• y is an integer between 30-85.
• the triblock copolymer is Pluronic ® P123, having
• the alkoxysilanes, organoalkoxysilanes, or combinations thereof are condensed on the substantially nonporous core in a solution comprising:
• the alkoxysilane used is selected from the group of tetramethoxsilane or tetraethoxysilane.
• the organosiloxane is selected from the group of phenyltriethoxysilane; phenyltrimethoxysilane; phenylethyltriethoxysilane;
• the alkoxysilane used is tetraethoxysilane and the organoalkoxysilane used is l,2-bis(triethoxysilyl)ethane.
• the concentration of octadecyltrimethylammonium bromide is maintained between 8-14 mM.
• the molar ratio of octadecyltrimethylammonium bromide and Pluronic ® P123 is maintained at or above 1.30.
• the molar ratio of alkoxysilane to organoalkoxysilane ranges between 30: 1 to 1 :30.
• alkoxysilane, organoalkoxysilane, or combinations thereof are prediluted in ethanol.
• prediluted ethanol solutions of alkoxysilane, organoalkoxysilane, or combinations thereof are added at a slow and constant rate to prevent fines generation, aggregation and agglomeration.
• prediluted ethanol solutions of alkoxysilane, organoalkoxysilane, or combinations thereof are added a rate between
• a secondary solution comprising ethanol, water, ammonium hydroxide, ionic surfactant and non-ionic surfactant is added at a slow and constant rate to prevent fines generation, aggregation and agglomeration.
• the secondary solution comprising ethanol, water, ammonium hydroxide, ionic surfactant and non- ionic surfactant is added within a range between the rate required to maintain a uniform ratio of particle surface area (m 2 ) to reaction volume, to the rate required to maintain a uniform ratio of particle volume (m 3 ) to reaction volume.
• the surfactant mixture is removed through one or more of the following; extractions with acid, water, or organic solvent; ozonolysis treatments, thermal treatments ⁇ 500°C, or thermal treatments between 500-1000°C.
• the surfactant mixture is removed through combination of acid extractions and ozonolysis treatments.
• each layer of porous shell material is applied using alkoxysilanes, organoalkoxysilanes, nanoparticles, polyorganoalkoxysiloxanes, or combinations thereof,: comprising the steps of:
• the alkoxysilane used is selected from the group of tetramethoxsilane or tetraethoxysilane.
• the organosiloxane is selected as one or more of the following from the group of phenyltriethoxysilane; phenyltrimethoxysilane;
• phenylethyltriethoxysilane phenylethyltriethoxysilane; phenylethyltrimethoxysilane; ethyltriethoxysilane;
• ethyltrimethoxysilane methyltriethoxysilane; methyltrimethoxysilane, diethyldiethoxysilane; diethyldimethoxysilane l,4-bis(triethoxysilyl)benzene; l,4-bis(trimethoxysilyl)benzene; 1,3- bis(triethoxysilyl)benzene; l,3-bis(trimethoxysilyl)benzene; l,8-bis(triethoxysilyl)octane; 1,8- bis(trimethoxysilyl)octane; l,2-bis(trimethoxysilyl)ethane; l,2-bis(triethoxysilyl)ethane; 1,2- bis(methyldiethoxysilyl)ethane; 1 ,2-bis(methyldimethoxysilyl)ethane; vinyl trie thoxysilane; vinyltrimethoxy
• the alkoxysilane used is tetraethoxysilane and the organoalkoxysilane used is octadecyltrimethoxysilane.
• the alkoxysilane, one or more organoalkoxysilanes, or combinations thereof are prediluted in ethanol.
• the prediluted ethanol solutions of alkoxysilane, one or more organoalkoxysilanse, or combinations thereof are added a slow and constant rate to prevent fines generation, aggregation and agglomeration.
• prediluted ethanol solutions of alkoxysilane, one or more organoalkoxysilanes, or combinations thereof are added a rate between 5-500 ⁇ ⁇ .
• a secondary solution comprising ethanol, water, and ammonium hydroxide is added at a slow and constant rate to prevent fines generation, aggregation and agglomeration.
• a secondary solution comprising ethanol, water, and ammonium hydroxide is added within a range between the rate required to maintain a uniform ratio of particle surface area (m 2 ) to reaction volume, to the rate required to maintain a uniform ratio of particle volume (m 3 ) to reaction volume.
• porosity is introduced through extraction, degradation, hydrolysis, deprotection, or transformation of the hybrid group through one or more of the following; extractions with acid, water, or organic solvent; ozonolysis treatments, thermal treatments ⁇ 500°C, or thermal treatments between 500-1000°C.
• porosity is introduced through extraction, degradation, hydrolysis, deprotection, or transformation of the hybrid group through combination of acid extractions, ozonolysis treatments and/or thermal treatments ⁇ 500°C.
• each layer is applied using a mixture of formula XX.
• D is one or more inorganic components upon initial condensation.
• E is one or more hybrid components upon initial condensation.
• F is one or more hybrid components upon initial condensation that can be further reacted to increase the porosity of the superficially porous layer
• the precursor for the inorganic component upon initial condensation (D) is selected from oxide, hydroxide, ethoxide, methoxide, propoxide, isopropoxide, butoxide, sec-butoxide, tert-butoxide, iso-butoxide, phenoxide, ethylhexyloxide, 2-methyl-2-butoxide, nonyloxide, isooctyloxide, glycolates, carboxylate, nitrate, chlorides, and mixtures thereof of silicon, titanium, zirconium, or aluminum.
• the precursor for the inorganic component upon initial condensation (D) is selected from tetraethoxysilane, tetramethoxysilane, methyl titanium triisopropoxide, methyl titanium triphenoxide, titanium allylacetoacetatetriisopropoxide, titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium trichloride, and zirconium methacryloxyethylacetoacetate tri-n-propoxide.
• the precursor for the hybrid component upon initial condensation (E) is selected from l,2-bis(triethoxysilyl)ethane, 1 ,2-bis(trimethoxysilyl)ethane, 1 ,4-bis(triethoxysilyl)benzene, 1 ,4-bis(trimethoxysilyl)benzene, 1 ,3-bis(triethoxysilyl)benzene, 1 , 3 -bis(trimethoxysilyl)benzene, 1,3,5 -tris(triethoxysilyl)benzene, 1,3,5- tris(trimethoxysilyl)benzene, and bis(4-triethoxysilylphenyl)diethoxysilane.
• the precursor for the hybrid component upon initial condensation that can be further reacted to increase the porosity of the superficially porous layer (F) is selected from phenyltrimethoxysilane, phenyltriethoxysilane,
• acetyloxyethyltrimethoxysilane acetyloxyethyltriethoxysilane; chloroethyltriethoxysilane; chloroethyltrimethoxysilane; methacryloxypropyltrimethoxysilane;
• methacryloxypropyltriethoxysilane bromoethyltrimethoxysilane; bromoethyltriethoxysilane; fluorotriethoxysilane; fluorotrimethoxysilane; and alkoxysilanes of the type:
• R was the corresponding octadecyl, dodecyl, octyl, 2-ethoxyethyl, or 3-ethyl-3-pentyl group
• v was an integer equal to 1- 4,
• porosity is introduced by reaction of hybrid group F through protodesilylation, hydrolysis, deprotection, acid extraction, thermal treatment ⁇ 500 °C, oxidation, ozonolysis or decomposition.
• Another aspect of the invention provides, a method to produce a core with increased hybrid content near the surface of the core by modifying a nonporous silica core with one more or more layers formed using an organosiloxane, a mixture of organosiloxane and alkoxysilane, polyorganoalkoxysilanes, a hybrid inorganic/organic surrounding material, or combination thereof.
• Still another aspect of the invention provides, a method to produce a superficially porous hybrid material that has increased hybrid content near the external surface of the material by modifying a superficially porous material with one more or more layers formed using an organosiloxane, a mixture of organosiloxane and alkoxysilane, polyorganoalkoxysilanes, a hybrid inorganic/organic surrounding material, or combination thereof.
• Yet another aspect of the invention provides, a method to produce a superficially porous hybrid particle that has increased hybrid content near the external surface of the particle by modifying a superficially porous particle with one more or more layers formed using an organosiloxane, a mixture of organosiloxane and alkoxysilane, polyorganoalkoxysilanes, a hybrid inorganic/organic surrounding material, or combination thereof.
• Still another aspect of the invention provides, a method to produce a superficially porous hybrid particle that has increased hybrid content near the external surface of the particle by modifying a superficially porous particle that is substantially silica (>90 molar%) with one more or more layers formed using an organosiloxane, a mixture of organosiloxane and alkoxysilane, polyorganoalkoxysilanes, a hybrid inorganic/organic surrounding material, or combination thereof.
• Still yet another aspect of the invention provides, a method to produce a superficially porous hybrid particle that has increased hybrid content near the external surface of the particle comprising the steps of
• a superficially porous particle that is substantially silica (>90 molar%) and has a pore volume between 0.18-0.50 cm 3 /g;
• the methods provide materials in which 1-15 layers are formed in the process. In other aspects, 2 -5 layers are formed. In still other 1-2 layers are formed.
• the superficially porous material is optimized by acid extraction, classification, ozonolysis treatment, hydrothermal treatment, acid treatment or combinations thereof.
• the superficially porous material is further surface modified.
• coating with a polymer by a combination of organic group and silanol group modification; a combination of organic group modification and coating with a polymer; a combination of silanol group modification and coating with a polymer; formation of an organic covalent bond between the material' s organic group and a modifying reagent; or a combination of organic group modification, silanol group modification and coating with a polymer.
• the invention provides a method for increasing the porosity of a substantially nonporous material comprising:
• the separations devices include, e.g., chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices and microtiter plates; packings for HPLC columns; solid phase extraction (SPE); ion-exchange chromatography; magnetic bead applications; affinity chromatographic and SPE sorbents; sequestering reagents; solid supports for combinatorial chemistry; solid supports for oligosaccharide, polypeptides, and/or oligonucleotide synthesis; solid supported biological assays; capillary biological assay devices for mass spectrometry, templates for controlled large pore polymer films; capillary chromatography; electrokinetic pump packing materials; packing materials for microfluidic devices; polymer additives; catalysis supports; and packings materials for microchip separation devices.
• materials of the invention can be packed into prepartory, microbore, capillary, and microfluidic devices.
• the materials of the invention impart to these devices improved lifetimes because of their improved stability.
• the invention provides a chromatographic column having improved lifetime, comprising
• a column having a cylindrical interior for accepting a packing material, and b) a packed chromatographic bed comprising a materials as described herein.
• the invention provides a chromatographic device, comprising
• a packed chromatographic bed comprising a materials as described herein.
• the invention also provides for a kit comprising the materials as described herein, as described herein, and instructions for use.
• the instructions are for use with a separations device, e.g., chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices, solid phase extraction device, microfluidic device, and microtiter plates.
• the %C, %H, %N values were measured by combustion analysis (CE-440 Elemental Analyzer;
• CM5300, CM5014, UIC Inc., Joliet, IL The specific surface areas (SSA), specific pore volumes (SPV) and the average pore diameters (APD) of these materials were measured using the multi-point N2 sorption method (Micromeritics ASAP 2400; Micromeritics
• Particle sizes were measured using a Beckman Coulter Multisizer 3 analyzer (30 ⁇ aperture, 70,000 counts; Miami, FL).
• the particle diameter (dp) was measured as the 50% cumulative diameter of the volume based particle size distribution.
• the width of the distribution was measured as the 90% cumulative volume diameter divided by the 10% cumulative volume diameter (denoted 90 /i 0 ratio).
• Light scattering particle size measurements were measured using a Malvern Mastersizer 2000 in water. Zeta- potential measurements were made using a Malvern ZetaSizer NanoSeries (model ZEN3600).
• Multinuclear ( 13 C, 29 Si) CP-MAS NMR spectra were obtained using a Bruker Instruments Avance-300 spectrometer (7 mm double broadband probe). The spinning speed was typically 5.0-6.5 kHz, recycle delay was 5 sec. and the cross-polarization contact time was 6 msec.
• Nonporous hybrid particles were formed following a modification of a reported process ⁇ Choi, J. Y.; Kim, C. H.; Kim, D. K. /. Am. Ceram. Soc, 1998, 81, 1184-1188. Seog, I. S; Kim, C. H. /. Mat. Sci., 1993, 28, 3277-3282 ⁇ . To a clean 40 mL vial was added a stir bar, water (26 mL) and 14.8 NH 4 OH (4.3 mL).
• This solution was then heated to 60 °C with stirring (600 rpm) in a water bath before one or more alkoxysilanes, including phenyltriethoxysilane (PTES, Gelest, Morrisville, PA), l,8-bis(triethoxysilyl)octane (BTEO, Gelest, Morrisville, PA), l,2-bis(triethoxysilyl)ethane (BTEE, Gelest, Morrisville, PA), 1,2- bis(methyldiethoxysilyl)ethane (BMDEE, Gelest, Morrisville, PA), vinyltriethoxysilane (VTES, Gelest, Morrisville, PA), or mercaptopropyltrimethoxysilane (MPTMS, Lancaster Chemical, Lancaster UK) were added (3 mL total).
• PTES phenyltriethoxysilane
• BTEO Triethoxysilyl)octane
• BMDEE 1,2- bis(methyldiethoxysilyl)ethan
• particles containing surface vinyl groups can be further reacted by the following transformation (not limited to); oxidation, polymerization, radical addition or metathesis.
• Particles containing surface thiol groups can be further reacted by the following transformation (not limited to); oxidation, radical addition, or disulfide bond formation.
• Particles containing surface phenyl groups can be further reacted by the following transformation (not limited to); protodesilylation or aromatic substitution.
• these nonporous hybrid materials are highly spherical particles that can have varying particle size distribution depending on synthetic conditions.
• Figure 1 contains SEM images of product lh and 11.
• Product lh clearly has a wider particle size distribution than product 11.
• the assessment of particle size distribution can also be made by determining the 90 /i 0 ratio. This approach is suitable to prepare products with 90 / 10 ratios ⁇ 1.20 and 90 / 10 ratios between 1.20-1.55. Differences in particle size distributions impacts packed bed structure and pressure of packed beds of chromatographic materials.
• Nonporous hybrid particles were formed following a modification of a reported process ⁇ US Patent 4,983,369 and 4,91 1,903 ⁇ .
• a stir bar To a clean Nalgene bottle (125 mL) was added a stir bar, water (14 mL), ethanol (80 mL), and NH 4 OH (7 mL, 14.8 M).
• TEOS tetraethoxysilane
• PTES phenyltriethoxysilane
• MPTMS mercaptopropyltrimethoxysilane
• the reaction was sealed and the onset of turbidity was monitored.
• the formation of spherical particles was further monitored over 24 h by light microscopy.
• the particles were purified and isolated by repeated centrifugation from ethanol (3 x 100 mL) and water (3 x 100 mL).
• the particles were air dried for 12 h and then vacuum dried (70 °C, 30 mm Hg) for 12 h.
• Carbon content was determined by combustion analysis. Average particle size was determined by SEM.
• organoalkoxysilanes All from Gelest Inc., Morrisville, PA or United Chemical Technologies, INC., Bristol, PA
• ethanol anhydrous, J.T. Baker, 5 Phillipsburgh, NJ
• 0.1 N hydrochloric acid Aldrich, Milwaukee, WI
• the oil phase solution was added into the EtOH/water/X100 mixture and was emulsified in the aqueous phase using a rotor/stator mixer (Model 100L, Charles Ross & Son Co., Hauppauge, NY). Thereafter, 30% ammonium hydroxide (44 mL, NH 4 OH; J.T. Baker, Phillipsburgh, NJ) was added into the emulsion. Suspended in the solution, the gelled product was transferred to a flask and stirred at 55 °C for 16h. Formed particles were isolated on 0.5 ⁇ filtration paper and washed consecutively with copious amounts of water and methanol (HPLC grade, J.T. Baker,
• Classification techniques can be used to isolate individual product fractions of desired size range (1-15 ⁇ ). This approach is suitable to prepare products with 90 /i 0 ratios ⁇ 1.20 and 90 /i 0 ratios between 1.20-1.55. Differences in particle size distributions impacts packed bed structure and pressure of packed beds of chromatographic materials.
• Non-porous particles are prepared by thermal treatment of porous silica and hybrid inorganic/organic particles in an air muffled oven at 1,000-1,200 °C for 20-40 hours.
• Example of porous hybrid particles included (but are not limited to) examples in Jiang ⁇ US 6,686,035; 7,223,473; 7,919,177 ⁇ and Wyndham ⁇ WO 2008/103423 ⁇ .
• the resulting nonporous silica products have no organic content. These materials maintain the general morphology and particle size distribution of the feed material. Average particle size decreases in this process. The degree of particle size decrease depends on the composition, density and porosity of the feed material. Any agglomerated materials are removed through grinding or classification. This approach is suitable to prepare products with / w ratios ⁇ 1.20 and / w ratios between 1.20-1.55. Differences in particle size distributions impacts packed bed structure and pressure of packed beds of chromatographic materials.
• rod shaped materials were prepared through the hydrochloric acid catalyzed hydrolysis of tetraethoxysilane (TEOS, Gelest, Morrisville, PA) in water in the presence of cetyltrimethyl ammonium chloride (CTAC, Aldrich, Milwaukee, WI). Products were collected on a filter and were washed with water and methanol. The products were dried under vacuum (80°C, 12h) and were submitted for SEM characterization.
• TEOS tetraethoxysilane
• CAC cetyltrimethyl ammonium chloride
• Differences rod lengths and thickness are an important variable that impacts packed bed structure and pressure of packed beds, alone or in a mixture with spherical particle packings.
• phenyltrimethoxysilane phenylethyltriethoxysilane
• phenylethyltrimethoxysilane phenyltrimethoxysilane
• ethyltriethoxysilane ethyl trimethoxysilane; methyltriethoxysilane; methyltrimethoxysilane diethyldiethoxysilane; diethyldimethoxysilane l,4-bis(triethoxysilyl)benzene; 1,4- bis(trimethoxysilyl)benzene; 1 ,3-bis(triethoxysilyl)benzene; 1 ,3-bis(trimethoxysilyl)benzene;
• methacryloxypropyltrimethoxysilane methacryloxypropyltriethoxysilane
• acetyloxyethyltrimethoxysilane acetyloxyethyltriethoxysilane; chloroethyltriethoxysilane; chloroethyltrimethoxysilane; fluorotriethoxysilane; or fluorotrimethoxysilane alone or in a mixture with tetraethoxysilane or tetramethoxysilane.
• Products were collected on a filter and were washed with water and methanol. The products are dried under vacuum (80°C, 12h) and are submitted for SEM characterization.
• Example 7 and 8 The porosity of products obtained in Example 7 and 8 are reduced by thermal treatment in an air muffled furnace at 700-1,200 °C for 10-72 hours. Isolation of sized samples and removal of any agglomerated materials is achieved through classification.
• Selected products from Examples 8 and 9, or porous silica (SSA between 5-1,000 m 2 /g; SPV between 0.1-1.6 cm 3 /g; and APD between 10-1000 A) and hybrid inorganic/organic particles (SSA between 5-1,000 m 2 /g; SPV between 0.1-1.6 cm 3 /g; and APD between 10-1000 A) are partially or completely pore filled with a mixture of one or more of the following; polymer, polymerizable monomer, silane, polyorganosiloxanes, or nanoparticles (5-200 nm) of diamonds, aluminum, gold, silver, iron, copper, titanium, niobium, zirconium, cobalt, carbon, silicon, silica carbide, cerium or any oxides thereof.
• ferromagnetic and ferrimagnetic nanoparticles includes (but is not limited to): magnetite (ferrous ferric oxide); maghemite; yttrium iron garnet, cobalt, Cr0 2 ; and ferrites containing iron and Al, Mg, Ni, Zn, Mn or Co). These magnetic materials allow for magnetic capture and processing of these materials.
• silanes and polyorganosilanes include (but are not limited to) those included in Example 4 and Jiang ⁇ US 6,686,035; 7,223,473; 7,919,177 ⁇ and Wyndham ⁇ WO
• Examples of polymers include latexes, epoxides, methacrylates, styrene, divinyl benzene, polysaccharides, dendrigrafts, hyperbranched polymers, and others included in Polymer Handbook ⁇ 4 edition, J. Brandrup; E. H. Immergut; E. A. Grulke; editors: Wiley: Hoboken, NJ, 1999 ⁇ .
• the filling of these porous particles can be performed by creating a mixture of additives in a solvent including (but not limited to) methylene chloride, water, acetone or ethanol followed by slow evaporation using an efficient rotary evaporator (0-78°C, 1- 24 h), to yield a free flowing powder.
• dry powder can be tumbled with additives in a polyethylene bottle at 0-100°C for 1-24 h), to yield a free flowing power.
• the powder produced can be washed with a suitable solvent including (but not limited to) ethanol or methanol.
• hydrolytic condensation can be performed using an aqueous solution of ammonium hydroxide and an alcohol, including (but not limited to) ethanol, isopropanol, or methanol. After stirring for 2-20 hours the product is collected on a filter and is washed with water and methanol or acetone. The product is dried under vacuum (80°C, 12h) and is submitted for SEM characterization.
• an alcohol including (but not limited to) ethanol, isopropanol, or methanol.
• polymerization is performed using an appropriate initiator including (but not limited to) free radical initiators, ring opening polymerization catalysts, metathesis catalysts, and living polymerization catalysts. After stirring for 2-20 hours the product is collected on a filter and is washed with water and toluene or acetone. The product is dried under vacuum (80°C, 12h) and is submitted for SEM characterization.
• an appropriate initiator including (but not limited to) free radical initiators, ring opening polymerization catalysts, metathesis catalysts, and living polymerization catalysts.
• Interval approaches of silanes or polyorganosiloxanes additives with polymer additives are performed as needed to further reduce porosity and increase amounts and types of additives in the pore structure.
• Layered or repeating structures of additives can be prepared by this approach. For example, a composite material containing both diamonds and magnetite would be beneficial for thermal conductivity improvements and magnetic capture processing.
• a material that contains alumina or titania is suitable for glycopeptides, phosphopeptide and phospholipids separations.
• a material that contains ceria may be suitable for phospholipid and phosphatidylcholines separations.
• Materials prepared by this approach are free flowing and maintain the general morphology and particle size distribution of the porous feed material.
• This approach is suitable to prepare products with 90 /i 0 ratios ⁇ 1.20 and 90 /i 0 ratios between 1.20-1.55. SPV decreases in this process.
• Exemplary products of this process are nonporous. The degree of porosity reduction depends on the amount of additives incorporated in the pore structure. Any agglomerated materials can be removed through grinding or classification.
• Composite materials of Example 10 are thermally treated at 700-1,200 °C for 10-40 hours to further reduce SPV. This thermal treatment is performed in air, under an inert atmosphere, or in a reducing atmosphere depending on compatibility of the additives employed. Materials containing diamond or magnetite employ an inert or reducing atmosphere is used to prevent oxidation.
• Materials prepared by this approach are free flowing and maintain the general morphology and particle size distribution of the porous feed material. SPV decreases in this process. Exemplary products of this process are nonporous. The degree of porosity reduction depends on the composition, density and porosity of the feed material. Any agglomerated materials can be removed through grinding or classification.
• spheroidal magnetite particles were prepared through the solvothermal reaction of iron trichloride.
• a mixture of anhydrous iron (III) chloride (Fisher Scientific), deionized water, ethylene glycol (Sigma-Aldrich, St. Louis, MO), polyethylene glycol (PEG 3400, Sigma- Aldrich, St. Louis, MO) and urea (Sigma-Aldrich, St. Louis, MO) were stirred at 50 °C until completely dissolved.
• the headspace was evacuated under vacuum and the pressure reactor was sealed before being heated (with or without stirring) to 220°C and was held at this temperature overnight.
• the reactor was cooled to ambient temperature.
• Products were isolated in a magnetic separator, and were washed by repeated resuspension in deionized water. Specific reaction data is provided on Table 6.
• Percent conversion of iron trichloride to magnetite was determined by iron concentrations analysis by digestion in hydrochloric acid and complexation with potassium thiocyanate. Magnetic properties were determined by VSM. Phase confirmation was determined by XRD. Particle size and standard deviation were determined by measuring individual particles by SEM (minimum particles counted > 60).
• Magnetite core particles (0.1-0.5 ⁇ ) from Example 12 are reacted with tetraethoxysilane in an aqueous ammonical ethanol solution following a general process described by Example 2, US Patent 4,983,369, US Patent 4,911,903, Giesche ⁇ /. Eur. Ceram. Soc, 1994, 14, 189; /. Eur. Ceram. Soc, 1994, 14, 205 ⁇ or Nozawa ⁇ Phys. Rev. E: Stat., Nonlinear, Soft Matter Phys., 2005, 72 (1), 011404 ⁇ .
• the product of this is a free flowing powder with a thick silica shell material. The final particle sizes for these materials are controlled between 0.8-1.7 ⁇ through changes in reaction conditions.
• Products are isolated by centrifugation, magnetic capture or filtration, and are washed with copious amounts of water and methanol.
• the product is air dried before drying under vacuum (80°C, 12h) and is submitted for SEM characterization. Any agglomerated materials can be removed through grinding or classification. Products prepared by this approach have little to no porosity.
• This silica layer on magnetite is advantageous because it reduces iron dissolution and reduces undesired secondary interactions between analytes and the magnetite surface during a chromatographic separation.
• Example 13 The process described in Example 13 is applied to other materials, including ones prepared in Examples 1-3, 5-11 as well as diamond, aluminum, gold, silver, iron, copper, titanium, niobium, zirconium, cobalt, carbon, silicon, silica carbide, cerium or any oxides thereof.
• the size of these materials is between 0.01-2.0 ⁇ . These materials can exist as dispersed particles or aggregates of nanoparticles.
• the silica layer thickness is controlled in this process through changes in reaction conditions and can produce final product sizes between 0.8- 5 ⁇ . Any agglomerated materials can be removed through grinding or classification. Products prepared by this approach are free flowing and have little to no porosity.
• Example 13 The process described in Example 13 is applied to other materials having non-spherical morphologies, including (but not limited to) spirals, capsules rings, discoidal, concave disks, spools, rings, helix, saddles, cross, cube, derby, helix, cylinders, and tubes.
• dumbbell, doughnut, rod, spiral, and gyroid shaped materials have been reported ⁇ Doshi, N. PNAS, 2009, 106, 51, 21495; Alexander, L. Chem. Commun., 2008, 3507; Naik, S. J. Phys. Chem. C 2007, 111, 11168; Pang, X. Microporous and Mesoporous Materials 2005, 85, 1; Kievsky, Y.
• Example 13-15 The process described in Example 13-15 is modified to replace tetraethoxysilane with one or more of the following (but not limited to): phenyltriethoxysilane;
• phenyltrimethoxysilane phenylethyltriethoxysilane
• phenylethyltrimethoxysilane phenyltrimethoxysilane
• ethyltriethoxysilane ethyltrimethoxysilane; methyltriethoxysilane; methyltrimethoxysilane diethyldiethoxysilane; diethyldimethoxysilane l,4-bis(triethoxysilyl)benzerie; 1,4- bis(trimethoxysilyl)benzene; 1 ,3-bis(triethoxysilyl)benzene; 1 ,3-bis(trimethoxysilyl)benzerie; 1 ,8-bis(triethoxysilyl)octane; 1 ,8-bis(trimethoxysilyl)octane; 1 ,2-bis(trimethoxysilyl)ethane; 1 ,2- bis(methyldiethoxysilyl)ethane; 1 ,2-bis(methyldimethoxysilyl)ethane; vinyl trie thoxysilane; vinyltrimethoxysilane;
• chloropropyltriethoxysilane chloropropyltrimethoxysilane; octadecyltrimethoxysilane;
• octadecyltriethoxysilane octyltrimethoxysilane; octyltriethoxysilane; 3,3.3- trifluoropropyltrimethoxysilane; 3 ,3.3 -trifluoropropyltriethoxysilane; 3- cyanobutyltriethoxysilane; and 3-cyanobutyltrimethoxysilane alone or in a mixture with tetraethoxysilane or tetramethoxysilane.
• the silica shell thickness is controlled in this process through changes in reaction conditions and can produce final product sizes between 0.8-1.7 ⁇ . Any agglomerated materials can be removed through grinding or classification. Products prepared by this approach are free flowing and have little to no porosity.
• Selected products in Example 13-16 are thermally treated at 700-1,200 °C for 10-72 hours to further reduce SPV.
• This thermal treatment is performed in air, under an inert atmosphere, or in a reducing atmosphere depending on the additives employed.
• an inert or reducing atmosphere is used to prevent oxidation.
• Materials prepared by this approach are free flowing and maintain the general morphology and size distribution of the porous feed material. SPV decreases in this process. Exemplary products of this process are nonporous. The degree of porosity reduction depends on the composition, density and porosity of the feed material. Any agglomerated materials can be removed through grinding or classification.
• PVP poly(vinylpyrrolidone)
• the alkoxysilanes used in Example 1 are modified to include substituted benzenes, including (but not limited to) l,4-bis(triethoxysilyl)benzene, l,4-bis(trimethoxysilyl)benzene, 1 , 3 -bis(triethoxysilyl)benzene, 1 ,3 -bis(trimethoxysilyl)benzene, 1,3,5- tris(triethoxysilyl)benzene, l,3,5-tris(trimethoxysilyl)benzene, and bis(4- triethoxysilylphenyl)diethoxysilane.
• substituted benzenes including (but not limited to) l,4-bis(triethoxysilyl)benzene, l,4-bis(trimethoxysilyl)benzene, 1 , 3 -bis(triethoxysilyl)benzene, 1 ,3 -bis(
• Bridging arylene materials have been shown to have improved thermal stability over traditional hybrid inorganic/organic materials ⁇ Shea, K. /. Non- Cry st. Solids, 1993, 160, 234 ⁇ . Particles prepared by this approach are spherical and free flowing.
• the alkoxysilanes used in Example 2 are modified to include substituted benzenes, including (but not limited to) l,4-bis(triethoxysilyl)benzene, l,4-bis(trimethoxysilyl)benzene, 1 , 3 -bis(triethoxysilyl)benzene, 1 ,3 -bis(trimethoxysilyl)benzene, 1,3,5- tris(triethoxysilyl)benzene, l,3,5-tris(trimethoxysilyl)benzene, and bis(4- triethoxysilylphenyl)diethoxysilane.
• Materials prepared by this approach are free flowing and have improved thermal stability over traditional hybrid inorganic/organic materials.
• Superficially porous silica layers are formed on selected hybrid core materials from Example 1, 2, 19 and 20 using a modified process described by Kirkland ⁇ US 20070189944; 20080277346 ⁇ .
• 0.8-1.7 ⁇ hybrid core materials are treated with a 0.1-0.5 wt% solution of one or more polyelectrolytes including (but not limited to):
• poly(diallydimethylammonium chloride, polyethylenimine and poly(allylamine hydrochloride) in water The molecular weight of these polyelectrolytes can vary between 2,000 and 500,000. These materials are washed with water using repeated centrifugation, before redispersing in water. A 2-10 wt% solution of silica sols (8-85 nm) is then added with mixing. These materials are washed with water using repeated centrifugation. This process of polyelectrolyte treatment followed by washing, silica sol treatment, and washing can be repeated until a final particle size is achieved. Final drying of product is performed in a vacuum oven or lyophilizer at ambient to elevated temperatures.
• Products prepared in this manner have both silica sols and polyelectrolyte on the core material.
• thermal treatment at temperatures greater than 500°C (10-20 hours) is employed.
• a second thermal treatment at 825-1000°C for 10-20 hours is employed.
• thermal treatments are performed in air, under an inert atmosphere, or in a reducing atmosphere depending on the additives employed.
• an inert or reducing atmosphere is used to prevent oxidation.
• the polyelectrolyte of Example 21 is modified to include the use of chemically degradable polymers, including (but not limited to) polyethylene glycol, polypropylene glycol, polymethacrylate, polymethylmethacrylate, poly( acrylic acid), and polylactic acid based polymers containing pendant primary, secondary, or tertiary amino groups.
• chemically degradable polymers including (but not limited to) polyethylene glycol, polypropylene glycol, polymethacrylate, polymethylmethacrylate, poly( acrylic acid), and polylactic acid based polymers containing pendant primary, secondary, or tertiary amino groups.
• PEG polyethylene glycol
• polyether amines are described in US 7,101,52, and others are commercially available as Jeff amine polyetheramines (Huntsman Corporation).
• Products prepared in this manner have both silica sols and polymer on the core material.
• different approaches are employed that do not require thermal treatment at or above 500°C.
• Polymethylmethacrylate networks can be decomposed using ⁇ -ray irradiation.
• Acrylate and methacrylate polymer backbones having thermally cleavable tertiary ester linkages can decompose between 180-200°C ⁇ Ogino, K. Chem. Mater, 1998, 10, 3833 ⁇ .
• Polyethylene glycol groups can be removed by oxidative degradation ⁇ Andreozzi, R. Water Research, 1996, 30, 12, 2955; Suzuki, J. J.
• Materials prepared by this process are free flowing spherical superficially porous particles with rough surface features, Expected improvements in chemical stability of a hybrid core in chromatographic applications are realized by this approach. Improvements in chemical stability of these superficially porous particles over commercially available silica superficially porous particles are achieved by this approach.
• the core material of Example 21 is modified to include the precursor or product materials from Examples 5-18. Included in this are spherical, irregular, rod-shaped and toroid- shaped materials. Included in this are 0.5-1.5 ⁇ cores that are diamond, magnetite, coated diamond, or coated magnetite.
• the core material of Example 22 is modified to include the precursor or product materials from Examples 5-18. Included in this are spherical, irregular, rod-shaped and toroid- shaped materials. Included in this are 0.5-1.9 ⁇ cores that are diamond, magnetite, coated diamond, or coated magnetite.
• the silica sol used in Examples 21-24 is modified to include the use of hybrid sols.
• Hybrid sols are prepared by the condensation of hybrid inorganic/organic alkoxysilanes in the presence or absence of a tetraethoxysilane or tetramethoxysilane. Similar sol sizes can be achieved in this approach (8-85 nm) by this approach.
• a hybrid layer can be formed by surface modifying preformed silica sols (8-85 nm).
• the use of a hybrid core material and chemically degradable polymers containing pendant primary, secondary, or tertiary amino groups described in Example 22, allows for the formation of hybrid superficially porous materials.
• 0.8-1.9 ⁇ ⁇ silica cores are used.
• Examples 21-25 is modified to replace a part of all of sols used with similar size sols, including (but not limited to) diamonds, aluminum, gold, silver, iron, copper, titanium, niobium, zirconium, cobalt, carbon, silicon, silica carbide, cerium or any oxides thereof.
• Examples 21-26 is modified to include incorporation of one or more nanoparticles within the superficially porous layer, including (but not limited to) nanoparticles listed in Example 10.
• Nonporous silica particles (1.26 ⁇ , 10.4 g), that were previously thermally treated at 600 °C (10 h) and rehydroxylated using 10% nitric acid (Fisher scientific) were dispersed in 80 mL of solvent (water: anhydrous ethanol 2: 1 v/v) by sonication for 10 minutes.
• solvent water: anhydrous ethanol 2: 1 v/v
• octadecyltrimethylammonium bromide (0.43 g, Ci 8 TAB, Sigma-Aldrich) was dissolved in 80mL of solvent (water: anhydrous ethanol 2: 1 v/v). The Ci 8 TAB solution was then added into the particle solution and was sonicated for 10 minutes. This solution was labeled solution A.
• the sample was diluted four times the sample volume with deionized water followed by centrifugation (Forma Scientific Model 5681, 2,500 rpm, 6 min). The wash sequence was repeated two times using sonication to redisperse particles.
• Nonporous silica particles (10.4 g, 1.26 ⁇ ), that were previously thermally treated at 600°C (10 h) and rehydroxylated using 10% nitric acid (Fisher scientific), were dispersed in 100 mL of solvent (water: anhydrous ethanol 2: 1 v/v) by sonicating for 10 minutes.
• solvent water: anhydrous ethanol 2: 1 v/v
• octadecyltrimethylammonium bromide (2.46 g, Ci 8 TAB, Sigma- Aldrich) was dissolved in 100 mL of solvent (water: anhydrous ethanol 2: 1 v/v).
• the Ci 8 TAB solution was then added into the particle solution and was sonicated for 10 minutes. This solution was labeled solution A.
• Example 28 The wash steps were performed as detailed in Example 28.
• the growth process was done once to grow a hybrid layer on the nonporous silica core. Reaction details are included on Table 8.
• Products were isolated by centrifugation and washed consecutively with copious amounts of water and methanol (HPLC grade, J.T. Baker, Phillipsburgh, NJ). The particles were then air dried and at 80 °C under vacuum for 16 hours. Products were submitted for SEM analysis. Particle size was determined by measuring individual particles by SEM. As shown in Table 8, and increase in Ci 8 TAB concentration (2.6-13.6 mM) results in an increase in shell thickness (0.04-0.16 ⁇ ) by this approach. Similar to Example 28, reactions using less than 3 mM CisTAB had increased aggregation and elevated amount fine particle ( ⁇ 1 ⁇ ) were observed. Concentrations of Ci 8 TAB between 8-17 mM were advantageously used to result in well formed products. TABLE 8
• An initial hybrid growth layer is formed on rehydroxylated nonporous silica particles (0.8-1.7 ⁇ , 10.4 g) using a modified process for Product 29b.
• These core particles can have 9 0 /io ratios ⁇ 1.20 or 90 /i 0 ratios between 1.2-1.55.
• the particle size is monitored during this growth process.
• the reaction is allowed to continue stirring until the target particle size is reached or all BTEE is added.
• the mixture is allowed to stir for an extra hour before the wash steps, which are performed as detailed in Example 28.
• Ci 8 TAB, Pluronic P123, ethanol, and ammonium hydroxide are made to maintain a low concentration of solids.
• Cig-TAB concentration is maintained between 8-1 1 mM, and the mol ratio of Cig-TAB Pluronic P123 was maintained at 1.3: 1.
• Optimization experiments showed that lower ratios of these two surfactants leads to increased aggregation.
• BTEE is diluted with anhydrous ethanol (dilution factor > 3) and is added to the reaction at a flow rate of 5-100 ⁇ / ⁇ . The particle size of these materials is monitored during this growth process. The reaction is allowed to continue stirring until the target particle size is reached or all BTEE is added. The mixture is allowed to stir for an extra hour before the wash steps, which are performed as detailed in Example 28.
• Products are isolated by centrifugation and are washed consecutively with copious amounts of water and methanol (HPLC grade, J.T. Baker, Phillipsburgh, NJ). The products are then air dried and at 80 °C under vacuum for 16 hours. Products are submitted for SEM, and FIB/SEM analysis. Particle size is determined by measuring individual particles by SEM. As listed in Table 9, final products have an average particle size of 1.2-2.7 ⁇ , with shell thickness varying from 0.03-0.60 ⁇ . Products prepared by this approach are free flowing, spherical and have a smooth surface. Products 30a, 30b, and 30g are prepared in one layer. Products 30c-f, 30-h-l are prepared in two to four growth layers. Products 30m-p are prepared in 5-15 layers.
• Products 30d and 30g (1.30 ⁇ ); Products 30e and 30 h (1.50 ⁇ ); Products 30f, 30i and 30 k (1.70 ⁇ ); and Products 30m and 30n (2.30 ⁇ ) have similar final particle size, but vary in shell thickness and the ratio of shell thickness to radius of the core.
• the ratio of shell thickness to core radius can be modified over a large range by this approach (0.04- 0.71).
• Examples 30 The process of Examples 30 is modified to have a superficially porous layer formed in a single continued growth layer using rehydroxylated nonporous silica particles (0.8-2.5 ⁇ ). These core particles can have 90 /i 0 ratios ⁇ 1.20 or 90 /i 0 ratios between 1.2-1.55.
• l,2-bis(triethoxysilyl)ethane (BTEE, Gelest)
• diluted with anhydrous ethanol 3
• a peristaltic pump ISMATEC, ISM596D equipped with 1/32 inch diameter PTFE tubing from Cole-Palmer
• octadecyltrimethylammonium bromide (CigTAB, Sigma- Aldrich), water, ethanol, Pluronic P123 (Sigma- Aldrich) and ammonium hydroxide solution (30%, 24 mL, J.T. Baker) is added using a separate peristaltic pump at a constant rate in order to maintain concentrations of Ci 8 TAB, water, ethanol, Pluronic P123, ammonium hydroxide within a range between the rate required to maintain a uniform ratio of particle surface area (m 2 ) to reaction volume, to the rate required to maintain a uniform ratio of particle volume (m 3 ) to reaction volume.
• the particle size of these materials is monitored during this growth process.
• the reaction is allowed to continue stirring until the target particle size is reached or all BTEE is added.
• the mixture is allowed to stir for an extra hour before the wash steps, which are performed as detailed in Example 28.
• Final products have an average particle size of 1.0-2.9 ⁇ , with shell thickness varying from 0.03-0.60 ⁇ .
• Products are submitted for SEM, and FIB/SEM analysis. Particle size is determined by measuring individual particles by SEM. Products prepared by this approach are free flowing, spherical and have a smooth surface. Analysis of particle by FIB/SEM shows evidence of a single step process, having no observable interlayer contrast.
• a silica layer was formed by the following process. Particles were dispersed in 80 mL of solvent (water: anhydrous ethanol 2: 1 v/v) by sonicating for 10 minutes. Separately, octadecyltrimethylammonium bromide (0.46 g, Ci 8 TAB, Sigma-Aldrich) was dissolved in 80 mL of solvent (water: anhydrous ethanol 2: 1 v/v). The Ci 8 TAB solution was added into the particle solution and the mixture was sonicated for 10 minutes. This solution was labeled solution A.
• a hybrid layer was formed on these particles using the following process. Particles were redispersed in 100 mL solvent (water: anhydrous ethanol 2: 1 v/v) by sonication.
• octadecyltrimethylammonium bromide (3.0 g, Ci 8 TAB, Sigma-Aldrich) was dissolved in lOOmL of solvent (water: anhydrous ethanol 2: 1 v/v). The Ci 8 TAB solution was then added into the particle solution and was sonicated for 10 minutes. This solution was labeled solution A.
• Pluronic P123 (58g, Sigma-Aldrich) was dissolved in 400 mL of solvent (water: anhydrous ethanol 2: 1 v/v) and was labeled solution B.
• Solution B 400 mL was added into solution A (200 mL) and allowed to continue to sonicate for 20 minutes.
• Example 28 The product was isolated and was washed as detailed in Example 28.
• a silica layer was then grown on the hybrid layer using the silica layer process described above, but the volume of the solution was increased to compensate for the increase in solids volume while maintaining a constant concentration of the reagents.
• a hybrid layer was formed on this silica layer using the hybrid layer process described above, but the volume of the solution was increased to compensate for the increase in solids volume while maintaining a constant concentration of the reagents.
• the first (product 32a) had a silica followed by hybrid layer.
• the second (product 32b) had a silica followed by two consecutive hybrid layers, resulting in an increased hybrid content near the exterior surface.
• Example 28-32 The process of Example 28-32 is modified to use tetraethoxysilane in the first layer followed by l,2-bis(triethoxysilyl)ethane or a mixture of tetraethoxysilane and 1,2- bis(triethoxysilyl)ethane in the following layer.
• This solution varies from 0-99 vol% tetraethoxysilane.
• This sequence is repeated (2-15 times) to create a distinct silica and hybrid layers. By changing reaction conditions the thickness of the silica porous layer and the hybrid porous layers can be modified between 10-1000 nm.
• composition of this 1,2- bis(triethoxysilyl)ethane and tetraethoxysilane mixture can vary for each layer, creating an enriched hybrid content at the external porous surface.
• composition of this 1,2- bis(triethoxysilyl)ethane and tetraethoxysilane mixture can vary for each layer, creating enriched silica content at the external porous surface.
• the composition of a mixed tetraethoxysilane and l,2-bis(triethoxysilyl)ethane solution can be modified by changing the feed alkoxysilane solution over the course of these reactions.
• Example 28-32 The process of Example 28-32 is modified to use l,2-bis(triethoxysilyl)ethane in the first layer followed by l,2-bis(triethoxysilyl)ethane or a mixture of tetraethoxysilane and 1,2- bis(triethoxysilyl)ethane in the following layer.
• This solution varies from 1-100 vol% tetraethoxysilane.
• This sequence is repeated (2-15 times) to create a distinct hybrid and silica layers. By changing reaction conditions the thickness of the hybrid porous layers can be modified between 10-1000 nm.
• composition of this l,2-bis(triethoxysilyl)ethane and tetraethoxysilane mixture can vary for each layer, creating an enriched hybrid content at the external porous surface.
• composition of this l,2-bis(triethoxysilyl)ethane and tetraethoxysilane mixture can vary for each layer, creating enriched silica content at the external porous surface.
• the composition of a mixed tetraethoxysilane and l,2-bis(triethoxysilyl)ethane solution can be modified by changing the feed alkoxysilane solution over the course of these reactions.
• the core material of Example 28-34 is modified to include the precursor or product materials from Examples 1-3, or 5-20. Included in this are spherical, irregular, rod-shaped and toroid-shaped materials. Included in this are 0.5-1.9 ⁇ cores that are hybrid, diamond, magnetite, coated diamond, or coated magnetite.
• Examples 28-35 is modified to replace a part of all of the alkoxysilane used with one or more of the following silanes (but not limited to) listed in Example 16 and 19, Jiang ⁇ US 6,686,035; 7,223,473; 7,919,177 ⁇ , Wyndham ⁇ WO 2008/103423 ⁇ , or a POS used in Example 4.
• Examples 28-36 is modified to replace a part of all of the alkoxysilane used with one or more of the following metal oxide precursors (but not limited to): the oxide, hydroxide, ethoxide, methoxide, propoxide, isopropoxide, butoxide, sec-butoxide, tert-butoxide, iso-butoxide, phenoxide, ethylhexyloxide, 2 -methy 1-2 -butoxide, nonyloxide, isooctyloxide, glycolates, carboxylate, nitrate, chlorides, and mixtures thereof of titanium, zirconium, iron, copper, niobium, cobalt, cerium or aluminum.
• the metal oxide precursors are methyl titanium triisopropoxide, methyl titanium triphenoxide, titanium
• methacryloxyethylacetoacetate triisopropoxide pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium trichloride, and zirconium
• Examples 28-37 is modified to include incorporation of one or more nanoparticles within the superficially porous layer, including (but not limited to) nanoparticles listed in Example 10.
• Examples 28-38 The process of Examples 28-38 is modified to add or replace part or all of the ionic and or non-ionic surfactants with one or more polyectrolyte or polymers detailed in Examples 21 or 22.
• the surfactants and or polymers used in select products from Examples 28-39 are removed by extraction in a 1-2 M solution of hydrochloric acid in methanol, ethanol or acetone, at elevated temperatures (30-90°C) for 1-20 hours. Products are isolated on isolated on 0.5 ⁇ filtration paper and washed consecutively with copious amounts of water and methanol (HPLC grade, J.T. Baker, Phillipsburgh, NJ). This process can be repeated 1-3 times to further remove surfactants and or polymers from these particles. Products are dried at 80 °C under vacuum for 16 hours and are submitted for carbon, CP-MAS NMR, SEM, and nitrogen sorption analysis. For products that contain hybrid content in the shell or porous layer, carbon content is present in the product.
• the surfactants and or polymers used in select products from Examples 28-40 are removed by ozonolysis in water at low to moderate temperatures (0-30°C) for 1-20 hours. Products are isolated on isolated on 0.5 ⁇ filtration paper and washed consecutively with copious amounts of water and methanol (HPLC grade, J.T. Baker, Phillip sburgh, NJ). This process can be repeated 1-3 times to further remove surfactants and or polymers from these particles. This process can be combined with an acid extraction approach detailed in Example 40. Products are dried at 80 °C under vacuum for 16 hours and are submitted for carbon, CP- MAS NMR, SEM, and nitrogen sorption analysis. For products that contain hybrid content in the shell or porous layer, carbon content is present in the product.
• the surfactants and or polymers used in select products from Examples 28-41 are removed by 500°C (10-20 hours) is employed. To further strengthen these superficially porous materials, increased thermal treatment at 825-l,000°C in air for 10-20 hours is employed.
• Products prepared by this approach are free flowing. Any agglomerated materials can be removed through grinding or classification.
• SSA specific surface areas
• SPV specific pore volumes
• hydrothermal treatment methods of Jiang ⁇ US 6,686,035; 7,223,473; 7,919,177 ⁇ or Wyndham ⁇ WO 2008/103423 ⁇ are employed.
• a material from Examples 28-39 are used that have a surfactant or polymer additive
• hydrothermal treatments are used to improve pore diameter.
• a surrounding material method described by Wyndham ⁇ WO 2010/141426 ⁇ can be used to strengthen these superficially porous materials.
• the surrounding material method is of particular importance when a hybrid inorganic/organic surrounding material is used on the silica superficially porous layer. In this instance, the hybrid inorganic/organic surrounding material reduces the porosity.
• Such materials have improved chemical stability over commercially available silica superficially porous particles.
• the surrounding material contains nanoparticles, including (but not limited to) nanodiamonds - as noted in Examples 12 and 13 of Wyndham ⁇ WO 2010/141426 ⁇ - improvements in thermal conductivity can be achieved.
• Products, after surfactant or polymer removal, have pore diameters between 60 A and 350 A.
• a series of superficially porous materials were prepared following a multi-step process: (1) Stober seeds preparation using tetraethoxysilane (TEOS); (2) core growth using TEOS; (3) hybrid layer growth using a mixture of TEOS and octadecyltrimethoxysilane (CigTMOS); (4) classification to remove fines; (5) calcination to introduce porosity; (6) pore processing steps; (7) re-calcination to improve mechanical strength; (8) rehydroxylation; and (9) surface bonding.
• TEOS tetraethoxysilane
• SigTMOS octadecyltrimethoxysilane
• the seeds were prepared by a modified Stober process. Uniform sized silica can be prepared (0.1-2.0 ⁇ ) depending on the concentration of TEOS, composition of the hydrolysis solution, temperatures, and mixing. In current studies, TEOS addition rate was fixed at 0.044 g/mL and hydrolysis solution consisted of ethanol, water and 30% ammonium hydroxide solution at volume ratio of 80/14/7, respectively. Increased mixing levels during seed formation resulted in higher content of aggregates. Optimal mixing conditions were determined to be initial vigorous shaking for 15 seconds before maintaining the reaction unstirred. This approach resulted in less than 5 wt% aggregates.
• the cores were further grown with concurrent additions of TEOS and hydrolysis solution (ethanol, waters, and ammonium hydroxide). Additional hydrolysis solution was added to prevent reseeding and aggregation/agglomeration events. Solvent conditions were optimized by exploring ternary phase diagrams to ensure the TEOS was miscible in the aqueous ethanol mixture. Typical addition rates of TEOS and the hydrolysis solution were set at 0.125 mL/min and 1 mL/min, respectively, and the reaction temperature was 50 °C. Core size was verified using light scattering, Coulter Counter, or SEM.
• the TEOS reservoir was switched to a mixture of CigTMOS and TEOS to grow a hybrid layer on the core particles.
• CigTMOS/TEOS varied from 1/4 to 1/9. Advantageous molar ratios are from 1/4 to 1/6. Due to differing solubility of CigTMOS and TEOS the relative addition rates of silanes and hydrolysis solution were adjusted to ensure miscibility. Conditions were based on the ternary phase diagrams of CigTMOS /TEOS mixtures, water and ethanol. The process was monitored by light scattering, Coulter Counter, and SEM. Table 11 details experiments performed in
• Classification was performed, if needed, to remove fines, aggregates and/or agglomerates.
• a variety of classification techniques e.g., sedimentation, elutriation, and centrifugation can be used to for this separation.
• Process C allowed for increases in pore volume (SPV) to be achieved (-0.1 cm 3 /g) along with small increases in APD ( ⁇ 50 A). Process A or B was also used after Process C to further increase pore diameter.
• OTCS octadecyltrichlorosilane
• ODDMCS octadecyldimethylchlorosilane
• Prototypes data is provided in Table 15. Surface coverage was determined by difference in %C data before and after surface modification. Products were further packed into chromatographic columns and evaluated for performance (e.g., van Deemter analysis). Table 15
• Example 45 (steps 1-4) is modified to include the precursor or product materials from Examples 1-3, or 5-20. Included in this are spherical, irregular, rod-shaped and toroid-shaped materials. Included in this are 0.5-1.9 ⁇ cores that are hybrid, diamond, magnetite, coated diamond, or coated magnetite. A further modification is not to include steps 5-9.
• Examples 45-46 The process of Examples 45-46 is modified to replace a part of all of the alkoxysilane used with one or more of the following silanes (but not limited to) listed in Example 16 and 19, Jiang ⁇ US 6,686,035; 7,223,473; 7,919,177 ⁇ , Wyndham ⁇ WO 2008/103423 ⁇ , or a POS used in Example 4.
• a further modification is not to include steps 5-9 of Example 45.
• Examples 45-47 is modified to replace a part of all of the alkoxysilane used with one or more of the following metal oxide precursors (but not limited to) listed in Example 37.
• a further modification is not to include steps 5-9 of Example 45.
• Examples 45-48 is modified to include incorporation of one or more nanoparticles within the superficially porous layer, including (but not limited to) nanoparticles listed in Example 10.
• a further modification is not to include steps 5-9 of Example 45.
• R was the corresponding octadecyl, dodecyl, octyl, 2-ethoxyethyl, or 3-ethyl-3-pentyl group
• v was an integer equal to 1- 4,
• Suitable precursors include (but are not limited to) the oxide, hydroxide, ethoxide, methoxide, propoxide, isopropoxide, butoxide, sec -butoxide, tert-butoxide, iso-butoxide, phenoxide, ethylhexyloxide, 2-methyl-2-butoxide, nonyloxide, isooctyloxide, glycolates, carboxylate, nitrate, chlorides, and mixtures thereof of silicon, titanium, zirconium, or aluminum.
• the precursors are selected from the precursors, but are not limited to) the oxide, hydroxide, ethoxide, methoxide, propoxide, isopropoxide, butoxide, sec -butoxide, tert-butoxide, iso-butoxide, phenoxide, ethylhexyloxide, 2-methyl-2-butoxide, nonyloxide, isooctyloxide, glyco
• tetraethoxysilane tetramethoxysilane
• methyl titanium triisopropoxide methyl titanium triphenoxide, titanium allylacetoacetatetriisopropoxide, titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium trichloride, and zirconium
• Suitable precursors include (but are not limited to) alkoxysilanes listed in Example 16 and 19, Jiang ⁇ US 6,686,035; 7,223,473; 7,919,177 ⁇ or Wyndham ⁇ WO 2008/103423 ⁇ .
• E is 1,2- bis(triethoxysilyl)ethane, l,2-bis(trimethoxysilyl)ethane, l,4-bis(triethoxysilyl)benzene, 1,4- bis(trimethoxysilyl)benzene, l,3-bis(triethoxysilyl)benzene, l,3-bis(trimethoxysilyl)benzene, l,3,5-tris(triethoxysilyl)benzene, l,3,5-tris(trimethoxysilyl)benzene, and bis(4- triethoxysilylphenyl)diethoxysilane.
• Suitable precursors include (but are not limited to) an alkoxysilane from Example 50, phenyltrimethoxysilane, phenyltriethoxysilane,
• acetyloxyethyltrimethoxysilane acetyloxyethyltriethoxysilane; chloroethyltriethoxysilane; chloroethyltrimethoxysilane; methacryloxypropyltrimethoxysilane;
• Reactions used to increase porosity include protodesilylation, deprotection, thermal treatment ⁇ 500 °C, oxidation or decomposition.
• Products employing alkoxysilanes from Example 50 can result in products with increased porosity layers through acid extraction (as detailed in Example 40) or ozonolysis (as detailed in Example 41).
• the resulting reacted material may include a hybrid group or silica.
• F includes a silane from Example 50 the produce is reacted by repeated acid extraction (as detailed in Example 40) to create a superficially porous layer.
• Selected materials from Examples 45-49 and 51 -52 are further processed following the processes described in Examples 40-44. Classification is performed if needed to improve the particle size distribution, removing any fines or agglomerated materials.
• Selected precursor and product core materials from Examples 1-3, or 5-20 are surface modified with an alkoxysilane that contains a basic group of equation 1 , using the surface modification methods of Jiang ⁇ US 6,686,035; 7,223,473; 7,919,177 ⁇ and Wyndham ⁇ WO 2008/103423 ⁇ .
• x is 0-3; advantageously 0;
• Y represents chlorine, dimethylamino, inflate, meihoxy, etlioxy, or a longer chain alkoxy group
• R represent a basic group, including (but not limited to) -NH2, -N(R' )H, -N(R')2 , -N(R')3 + ,
• R' independently represents an alky!, branched alkyi, aryi, or cycloalkyl group; m is 2-6.
• Selected precursor and product core materials from Examples 1-3, or 5-20 are surface modified with an alkoxysi!ane that contains a basic group of equation 2, using the surface modification methods of Jiang ⁇ US 6,686,035; 7,223,473; 7,919,177 ⁇ and Wyndham ⁇ WO 2008/103423 ⁇ .
• x is 0-3; advantageously 0;
• Y represents chlorine, dimethylamino, inflate, methoxy, ethoxy, or a longer chain alkoxy group
• A represent an acidic group, including (but not limited to) a sulfonic acid, carboxylic acid, phosphoric acid, boronic acid, arylsulfonic acid, arylcarboxyiic acid,
• R' independently represents an alkyi, branched alkyi, aryi, or cycloalkyl group.
• Selected nanoparticulate materials detailed in Examples 10, 12, 14, 21, 22, 25, 26, 27, 37, and 38 are surface modified with an alkoxysilane that contains a basic group of equation 1 or 2, using the surface modification metiiods of Jiang ⁇ US 6,686,035; 7,223,473; 7,919,177 ⁇ and Wyndham ⁇ WO 2008/103423 ⁇ .
• Selected surface modified core materials in Example 54 and 55 are reacted with surface modified nanoparticulate materials in Example 56 using a modified process detailed in Example 21. In this approach no polyelectrolyte is used.
• a positively charged surface modified core material from Example 54 is used, a negatively charged nanoparticulate material from Example 56 is used.
• a positively charged nanoparticulate material from Example 56 is used.
• this single layered material can be used as is.
• additional layers can be added. These can be achieved by repeating this layering process using a nanoparticulate material from Example 56 of opposite charge from the last surface layer.
• the last surface layer used positively charged nanoparticulate material from Example 56 the following layer uses a negatively charged nanoparticulate material from Example 56.
• the last surface layer uses a negatively charged nanoparticulate material from Example 56 the following layer uses a positively charged nanoparticulate material from Example 56.
• This sequence of alternating charge nanoparticulate material can be used to form 2-15 layers on the core material. In this approach no polyelectrolyte material used.
• the type of nanoparticulate material used can vary between layers or remain the same. Eor example, a silica layer can be layered between diamond or magnetite layers by this approach.
• SSA specific surface areas
• SPV specific pore volumes
• products are thermally treated at 700-1,000 °C for 10-40 hours to further strengthen these superficially porous materials.
• This thermal treatment is performed in air, under an inert atmosphere, or in a reducing atmosphere depending on compatibility of the additives employed.
• Materials containing diamond or magnetite employ an inert or reducing atmosphere is used to prevent oxidation.
• the process of 57 is modified to introduce a polyelectrolyte or polymer material from Example 21-27.
• a polyelectrolyte or polymer material from Example 21-27.
• the last layer used a positively charged nanoparticulate material
• the following polyelectrolye or polymer used is negatively charged.
• the last layer used a negatively charged nanoparticulate material
• the following polyelectrolye or polymer used is positively charged.
• EXAMPLE 59 The process of 57-58 is modified to introduce layers formed with polyelectrolyte and layers formed without polyelectrolyte.
• the process of 57-59 is modified to use charged nanoparticulate materials that have been charged modified through acid or base washing, or electrostatically.
• the charge of these nanoparticulate materials can be monitored through zeta-potential measurements.
• the process of 57-60 is modified to hybrid core materials that have surface acid or base groups.
• Surface acidic groups can be prepare using hybrid core materials of the type described in Example 1-3 and 5 using phenyltriethoxysilane, or mercaptopropyltrimethoxysilane.
• the phenyl groups can be sulfonated by heating in sulfuric acid.
• the mercaptopropyl group can be oxidized to sulfopropyl groups using hydrogen peroxide or nitric acid.
• the use of a protected aminopropyl group in a hybrid core material of the type described in Example 1-3 and 5 can be used to create surface basic groups. Methyl iodide treatment of these amino groups can be used to prepare dimethyl and trimethyl aminopropyl groups.
• the process of 57-61 is modified to use hybrid nanoparticulate materials that have surface acid or base groups of the type detailed in Example 61.
• Select materials from Examples 21-43, 45-49, 51-52, and 57-61 are further processed following the processes described in Examples 40-44. Classification is performed if needed to improve the particle size distribution, removing any fines or agglomerated materials.
• Materials can be further treated by sedimentation in acetone to remove fines material.
• the products are dried at 80°C under vacuum for 16 h.
• Superficially porous materials prepared by this approach are submitted for analysis.
• the specific surface areas (SSA) and specific pore volumes (SPV) of these materials are increased with respect to the core materials.
• SPV vary between 0.08-0.45 cm 3 /g and average pore diameter varies between 60-300 A.
• Particle size measurements and SEM analysis indicate the formation of thick superficially porous layer. This 5 porous layer thickness varies between 0.07-0.53 ⁇ , material average size varies between 1.2- 15.0 ⁇ , and the product size distribution ( 90 /i 0 ratio) are similar to the size distribution of the core materials.
• the surface roughness of these materials varies from rough to smooth. Rough surfaces generally formed from sol-based approaches.
• the product shape generally resembles the core materials. For 10 example, when the cores are spherical, products are spherical. When cores are rod-shaped, products are rod-shaped. The noticeable difference is these products is a rounding of rough edges for jagged or flat faced core materials after the porous layer is formed.
• Products of this process are spherical having differences in particle size, distribution, 25 surface morphology, shell thickness and composition.
• Products 65a-65h detail the different final particle size, 90 /i 0 ratio, and surface roughness that can be achieved in this process while maintain a comparable ratio of shell thickness to radius of the core material (0.53).
• Products 651-651 have different ratios of shell thickness to radius of the core material (0.29-0.64), while maintaining a comparable final product particle size. These materials can be compared further 30 with Products 65a and 65b.
• Products 65m-65s have comparable particle size, distribution, morphology, shell thickness and ratio of shell thickness to radius core as Product 65a, but vary in composition (0-100% hybrid) in both the core and porous layer.
• composition Core Core ' 10 Layer Surface Particle Thickness Shell (x,y) Size ratio Composition Size ( ⁇ ) Thickness ( ⁇ ) (x,y) ( ⁇ ) to Radius
• SM Smooth Surface
• RS Rough Surface
• Products 67a-671 have different magnetite core size, coated core 90 /i 0 ratio, and surface roughness, while having a comparable porous layer composition.
• Products 67m-67t have differences in the hybrid and nanodiamond content of the porous layer.
• Example 65 Table 19 contains a description of these Cig-bonded materials. These products contain rod shaped core materials. Rod shaped cores are described with a length to width
• SM Smooth Surface
• RS Rough Surface
• CSD Cross Sectional Diameter
• CCSR Core Cross Sectional Radius.
• Product 68a-l have changes in average core rod length (1-3 ⁇ ) and average core rod cross sectional diameter (CSD, 1 -2 ⁇ ) and surface roughness, while having a comparable ratio of shell thickness to core rod cross sectional radius (CCSR).
• Products 68m-68p have changes in shell thickness to cross sectional radius and surface roughness, while having comparable core rod length and core rod CSD. These products can be compared with 68a-b.
• Products 68q-ac have changes in composition of the core rod and porous layer, while other parameters are
• SM Smooth Surface
• RS Rough Surface
• OD outer diameter
• ID Inner Diameter
• CSD Cross Sectional Diameter
• CCSR Core Cross Sectional Radius.
• Product 69a-g have changes in average product OD (1.63-8.06 ⁇ ), average core OD (1.5-7 ⁇ ) and core CSD (0.5-2 ⁇ ), while having a comparable ratio of shell thickness to core cross sectional radius (CCSR, 0.53).
• Products 69h-k have changes in ratio of average shell thickness to CCSR (0.3-0.6) and surface roughness, while having comparable average core OD and average core CSD. These products can be compared with 69d.
• Products 691-p have changes in composition of the porous layer, while other parameters are comparable to Product 69d. TABLE 20

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