Patent Grant
11731312
Methods for slip casting ceramic bodies in molds with the assistance of pressure and/or vacuum are known.
Commonly owned U.S. Pat. No. 9,790,125, incorporated herein by reference in its entirety, discloses a vacuum-assisted slip casting process, and vacuum-assisted slip casting assembly comprising a porous casting substrate surrounded by a removable enclosure, comprised of an impermeable materials, such as plastic, within which the ceramic blank forms.
EP 0 587 160 to Awazu discloses slip casting ceramics in a high strength mold made wholly or partially of porous metal or porous ceramic to carry out slip a casting process at higher pressure compared to conventional processes. The porous mold may have holes having a maximum diameter of the twenty times the diameter of the secondary particles of the powders in the slurry.
Methods and apparatus are provided to cast ceramic bodies from a slurry or suspension of micron and nano-sized zirconia ceramic powder. An apparatus that is adaptable to a pressure casting process, a vacuum casting process, or simultaneous pressure and vacuum casting process, is provided. The apparatus is also adaptable for casting in a single direction (axial or radial) or dual direction (axial and radial), by removing, adding, or substituting components that selectively block the flow of a ceramic suspension during the casting process.
Through processes described herein, ceramic bodies may be cast from ceramic micron-sized powder at an accelerated rate. Further, ceramic bodies may be cast from a suspension of nano-sized zirconia powder having large dimensions not previously achieved.
A casting apparatus may comprise an upper casting assembly and a lower casting assembly. An upper casting assembly comprises a slurry chamber and a mold. The slurry chamber and mold may be one piece, such as a cylinder, optionally having a divider to separate the slurry chamber from the mold. A lower casting assembly comprises a casting substrate on which ceramic buildup occurs above a support body. The mold is in communication with the casting substrate of the lower casting assembly. A vacuum may be applied to the bottom of the support body of the lower casting assembly pulling the suspension in the axial direction, the radial direction, or both.
For single direction, axial casting, liquid from the ceramic suspension is evacuated through the casting substrate, and the suspension liquid is prevented from moving in the radial direction through vertical walls of the mold. In one embodiment of a single direction, axial casting process, the mold walls comprise impermeable material to prevent radial movement of liquid during the casting process.
In one embodiment of a single direction, radial casting process, the flow of liquid in the axial (z-axis) direction through the bottom of the mold adjacent the casting substrate may be inhibited or blocked. For example, vacuum pressure through the casting substrate may be blocked by use of a non-porous casting substrate, non-porous support body, or both, comprised of material that is impermeable to the flow of liquid and air during vacuum casting conditions. Alternatively, a sheet or body of blocking material that is impermeable to the vacuum, air, and slurry, may be placed between the vacuum source and a porous casting substrate.
For radial casting (either a single direction radial casting or dual direction axial-radial casting), the walls of the mold may comprise mold wall openings, such as through holes, that allow the flow of liquid from the suspension through the vertical sides of the mold. A porous vertical body may surround the outer surface of the mold wall opposite the mold cavity, filling or covering the mold wall openings. Liquid from the ceramic suspension is discharged from the mold cavity through the mold wall openings and into the porous vertical body. A casting substrate and support body may also be comprised of a porous material that is the same or different from the porous vertical body.
Casting speed during radial casting may be controlled by the size of the through holes in the mold wall. Through holes may be uniform in size and shape, or a mold wall may have multiple sized openings. The openings may be any shape such as circular, rectangular, diamond, and the like, having a width or diameter of, for example, about 0.1 mm to 15 mm. The through holes in the impermeable mold material may comprise up to 95% of the surface area of the walls of the mold cavity. The perimeter of the mold that contacts a casting substrate during a casting process may comprise a solid band of impermeable material with no through holes for a portion of the vertical wall height. In this embodiment, the mold wall is impermeable around the perimeter adjacent the casting substrate for a height of at least 1.0 mm when measured from the casting surface. In one embodiment, when assembled with a casting substrate, the solid band of the mold cavity fits within an indentation of the support body that restricts movement of the mold during the casting process.
Upper and lower casting assemblies may further comprise an impermeable upper case and lower case fitted around upper and lower casting assemblies to restrict the flow of air, vacuum, and liquid through the casting assemblies, and to maintain pressure within the casting apparatus. The upper case may surround the outside of the porous vertical body and the mold. In one embodiment, the upper casting assembly comprises a gap between the upper case and the porous vertical body. During a vacuum casting process, pressure is reduced in the gap adjacent the porous vertical body, and liquid is evacuated radially through openings in the mold wall, through the porous vertical body, and into the gap to be eliminated from the casting apparatus. Suspension liquid may be eliminated through channels in the lower casting body that align with the gap, and then, evacuated out of the casting apparatus.
The casting apparatus may be adaptable to pressure casting. In one embodiment, the slurry chamber and mold may be made of a material having sufficient strength to withstand the application of positive pressure during the pressure casting process, such as metal (e.g., aluminum). A metal lid may be provided to cover the slurry chamber, attaching to the slurry chamber by attachment means such as latches or screws extending through holes. The lid may comprise inlets for a hose or nozzle to deliver the ceramic suspension and for delivering pressurized gas to the mold cavity, and optionally, for placement of a pressure gauge and/or pressure-releasing valve.
In one embodiment, casting processes may result in uneven buildup of ceramic material, where ceramic buildup is higher adjacent the wall of the mold and lower in the center of the cast body. Thus, in a further embodiment, a separator, such as a ring, may be located at the top of the mold, between the mold and the slurry chamber to prevent excess ceramic buildup around the outer edge of the cast body beyond the height of the separator. The separator may be a permeable divider between the mold and the slurry chamber, or a solid, impermeable ring around the perimeter of the mold having a permeable center portion that allows ceramic suspension to be introduced through openings in the permeable separator. Openings through the thickness of the permeable separator may be uniformly distributed across its surface to provide vacuum or pressure uniformly distributed over the ceramic body during casting.
In one embodiment, a dual vacuum-pressure casting apparatus is provided that may be configured to operate in nine different modes: 1) axial direction under vacuum, 2) axial direction under positive pressure, 3) axial direction under vacuum and positive pressure, 4) radial direction under vacuum, 5) radial direction under positive pressure, 6) radial direction under vacuum and positive pressure, 7) radial and axial directions under vacuum, 8) radial and axial directions under positive pressure, and 9) radial and axial directions under vacuum and positive pressure.
Casting processes described herein significantly reduce casting time of ceramic bodies compared to known vacuum casting processes.
Methods and apparatus are provided for slip casting ceramic bodies in a mold. The casting process may comprise a vacuum casting process, a pressure casting process, or both vacuum and pressure casting. Casting may be selectively unidirectional, in either the axial direction or radial direction_ or multi-directional in both axial and radial directions. A mold is provided that is adaptable to pressure casting or vacuum casting, in axial and/or radial directions. By processes described herein ceramic bodies may be cast from ceramic suspensions comprising zirconia nano-powder or micron-sized powder. The resulting cast ceramic bodies may be heated to form a pre-sintered (bisque) stage millable block, or fully sintered ceramic body. Solid ceramic bodies may be used as dental mill blocks that accommodate single or multi-unit restoration bodies, including, but not limited to crowns, veneers, bridges, dentures, and the like.
With reference to
In
The mold 204 comprises a mold cavity 207 having a first end 208 in communication with a slurry chamber 203 and a second end 209 in communication with casting substrate 205 when assembled with the lower casting assembly. A mold wall 210 that defines the mold cavity 207 is comprised of an impermeable material that is resistant to penetration of the liquid component of a ceramic suspension under casting vacuum and pressure. The impermeable material may be comprised of, for example, a polymer, metal or ceramic material. The thickness of the mold wall may be from 0.3 mm to 20 mm, or from 1 mm to 10 mm. The mold cavity comprises mold wall openings 211, or through holes, that extend through the thickness of the impermeable material of the mold wall 210.
As illustrated in
In one embodiment, the casting apparatus 200 comprises an upper case 214 (
The upper case 214 may surround the outer surface of the porous vertical body 212 in a spaced arrangement forming a gap 216 (
The casting substrate 205 may comprise a porous material having an average pore size sufficiently small to inhibit ceramic particles in the ceramic suspension from entering into the pore volume of the casting substrate during the vacuum/pressure casting process while evacuating the liquid component of the suspension. In one embodiment, a porous casting substrate 205 has an average pore size of less than 1 μm. The porous casting substrate may be comprised of, for example, a porous ceramic, such as plaster, a porous metal, or a porous polymer. In one embodiment, the porous casting substrate is the upper surface of the porous support body. In another embodiment, the porous casting substrate and the support body are separate components that are assembled in stacked configuration for the casting process. The support body and/or the porous vertical body may be made of a porous ceramic (e.g. plaster such as gypsum), porous metal, or porous polymer material, that is the same or different material of the porous casting substrate.
In one embodiment, a radial casting process is used to evacuate liquid through mold wall openings, in the absence of axial casting. The flow of liquid through the bottom end 209 of the mold in the axial (z-axis) direction may be inhibited by blocking vacuum pressure through the casting substrate 205. In this embodiment, the casting substrate 205, the support body 206, or both, may be non-porous, or may comprise material that is impermeable to the flow of liquid and air during vacuum casting conditions. In one embodiment, as illustrated in
Where a casting process is in the axial-only casting direction, evacuation of liquid from the suspension through mold wall openings is inhibited to prevent radial casting. In one embodiment, as illustrated in the bottom perspective view of the lower casting assembly of
In
An upper case 302 may be provided that surrounds the metal mold and, optionally, slurry chamber; to restrict the flow of air, vacuum, and liquids, and to maintain pressure within the casting apparatus during a dual pressure-vacuum casting process. The upper case may be, for example, metal or plastic. As seen in an illustration of an exploded view, a lid 303 covers the slurry chamber 301 when assembled, and may be attached to a flange 304 at the top of the slurry chamber 301. Attachment means, such as latches or screws extending through holes 305 on the lid 303 and flange 304 are capable of securing the apparatus under positive pressure. As illustrated in the top-down view of
As illustrated in a bottom-up view of
In exemplary embodiments illustrated in
The open area in the mold wall formed by the openings 405 may comprise up to 95% of the area of the vertical walls surrounding the mold cavity (404, 404′ and 404″). In one embodiment, mold wall openings are from 1 mm to 10 mm in diameter (or width), and the open area formed from a plurality of the mold wall openings is about 1% to 70%, or 2% to 50%, or 2% to 30% of the mold wall. In another embodiment illustrated in
A porous vertical material 406, such as a porous plaster, may surround the outside of the mold (e.g., 404, 404′ or 404″), as illustrated in
In one embodiment, as illustrated in
In one embodiment, the mold 404 and the slurry chamber 403 are separated, for example, by a permeable divider or a ring. As illustrated in the top down view of the cylinder 400 of
In an alternative embodiment, as illustrated in the casting apparatus 500 of
With reference to
A release agent may be applied to one or more surfaces of the mold cavity to facilitate removal of the cast ceramic body from the mold. Release agents include but are not limited to lubricants such as petroleum jelly, oleic acid, and the like, (e.g., Slide® Pure Eze Mold Release by Slide Products, Inc. IL, USA) that are at least partially insoluble under casting conditions. In some embodiments, approximately 1 psi or greater, such as 3 psi to 30 psi, may be applied by mechanical piston, or compressed gas, such as compressed air for a quick ejection of a cast ceramic body from the mold. In one embodiment, the upper and lower casting assembly are separated and compressed is delivered into the mold cavity, for example via one or more hoses, fittings, nozzles through the upper casting assembly.
Ceramic particles used in the suspensions may comprise, but are not limited to, alumina, zirconia, boron carbide, silicon carbide, spinel, and barium titanate, and other ceramic materials suitable for use in dental restorations, such as crowns, veneers, bridges and dentures. In some embodiments, ceramic material may comprise zirconia, alumina, or combinations thereof. Zirconia ceramic material may comprise unstabilized or stabilized (including partially stabilized or fully stabilized) zirconia ceramic material.
In some embodiments, zirconia ceramic powders include zirconia that has been stabilized with yttria. For example, yttria-stabilized zirconia may be stabilized with approximately 0.1 mol % to approximately 8 mol % yttria, such as approximately 2 mol % to 7 mol % yttria, or approximately 2 mol % to approximately 4 mol % yttria, or approximately 4 mol % to approximately 6 mol % yttria. Specific examples of yttria-stabilized zirconia powders include yttria-stabilized zirconia commercially available from Tosoh USA, such as Tosoh TZ-3YS (containing approximately 3 mol % yttria, nominally 3Y), Tosoh PX485 (containing approximately 4 mol % yttria, nominally 4Y), and Tosoh PX430 (containing approximately 5 mol % to 6 mol % yttria, such as nominally 5.5Y). Commercially available zirconia powder may have a measured particle size D(50) of about 600 nm or more, which constitute agglomerations of particles of crystallites having an actual particle size of about 20 nm to 40 nm.
As used herein, the term “measured particle size” refers to measurements obtained by a Brookhaven Instruments Corp. X-ray disk centrifuge analyzer. As used herein, the term “micron-size” zirconia may include zirconia ceramic having an average (D(50)) measured particle size greater than 100 nm, such as, between 100 nm and 1000 μm, or between 200 nm and 500 μm, or between 200 nm and 500 nm. In some embodiments, comminution processes described herein may to reduce the measured particle size of zirconia powder contained in the suspension, for example, from D(50)<600 nm, to a range of D(50)=100 nm to 400 nm, such as D(50)=200 nm to 300 nm. As used herein, the term “nano-size” zirconia may include zirconia ceramic having an average particle size less than 100 nm, such as between 20 nm and 70 nm.
Yttria-stabilized zirconia powders may further comprise alumina at a concentration of 0 wt % to 0.25 wt %, such as 0.1 wt %, relative to the zirconia powder. Optional additives include coloring agents and esthetic additives, such as metal oxides and metal salts, or other metal-containing compounds used to obtain dentally acceptable shades in final sintered restorations. In some embodiments, further processing aids such as binders and dispersants may be added to the suspension.
Dispersant may be used to promote dispersion and stability of the suspension, and to control the viscosity of the slip, during the casting process. Dispersion and deflocculation may occur through electrostatic, electrosteric, or steric stabilization. Examples of suitable dispersants include nitric acid, hydrochloric acid, citric acid, diammonium citrate, triammonium citrate, polycitrate, polyethyleneimine, polyacrylic acid, polymethacrylic acid, polymethacrylate, polyethylene glycols, polyvinyl alcohol, polyvinyl pyrillidone, carbonic acid, and various polymers and salts thereof. These materials may be purchased commercially or prepared by well-known techniques. Specific examples of commercially available dispersants include Darvan® 821-A ammonium polyacrylate dispersing agent commercially available from Vanderbilt Minerals, LLC; Dolapix™ CE 64 organic dispersing agent and Dolapix™ PC 75 synthetic polyelectrolyte dispersing agent (commercially available from Zschimmer & Schwarz GmbH), and Duramax™ D 3005 ceramic dispersant (commercially available from Rohm & Haas Company).
The liquid component of the ceramic suspension may comprise water, organic solvent, inorganic solvent, or a combination, thereof. A ceramic suspension may comprise a solid ceramic loading of between 40 wt % and 90 w %, or between 45 wt % and 80 w %, based on the total weight of the ceramic suspension. Upon adding zirconia powder and dispersant to the liquid component, the suspension may be subjected to a comminution process by which the zirconia powder particles are mixed, deagglomerated, and/or reduced in size. Comminution is performed using one or more milling processes, such as attritor milling, horizontal bead milling, ultrasonic milling, or other milling or comminution process, such as high shear mixing, ultra high shear mixing capable of reducing the zirconia powder particle sizes described herein. The resulting ceramic dispersion or suspension may be cast in the casting apparatus by processes described herein.
In one embodiment, a casting apparatus is provided that is adjustable for casting a zirconia ceramic suspension in nine modes: 1) axial direction casting under vacuum, 2) axial direction casting under positive pressure, 3) axial direction casting under vacuum and positive pressure, 4) radial direction casting under vacuum, 5) radial direction casting under positive pressure, 6) radial direction casting under vacuum and positive pressure, 7) radial direction and axial direction casting under vacuum, 8) radial direction and axial direction casting under positive pressure, and 9) radial direction and axial direction casting under vacuum and positive pressure. Vacuum pressure, positive pressure or both, may be selectively introduced into the casting assembly to optimize casting conditions.
In one embodiment, a method for making a solid ceramic block by dual direction (radial and axial directions) vacuum-pressure casting, comprises; i. providing a dual vacuum-pressure casting apparatus that comprises a slurry chamber, a mold having mold wall openings, and an impermeable ring within the mold between the slurry chamber and the mold; a porous casting substrate, a porous supporting body, and a porous vertical body, wherein the porous vertical body surrounds the outer surface of the mold; ii. delivering a ceramic suspension into the mold through the slurry chamber and applying both vacuum and positive pressure to the casting apparatus; in casting the suspension on the casting substrate and the mold wall; iv. discharging liquid from the ceramic suspension through the mold wall openings into the porous vertical body and through the porous casting substrate; iv. consolidating ceramic particles forming a ceramic green body within the mold cavity; v. separating the porous casting substrate from the mold to expose a mold opening; and vi. ejecting the resulting ceramic green body from the mold opening.
In vacuum casting processes, casting in a radial-only direction may be accomplished by blocking vacuum through the casting substrate thereby preventing or reducing flow in the axial direction and increasing flow radially through the mold wall openings and porous vertical body. In contrast, vacuum casting in an axial-only direction may be accomplished by blocking vacuum adjacent the porous vertical body, thereby preventing or reducing flow radially through mold wall openings, and increasing flow axially through the porous casting substrate. For example, an impermeable material, such as a gasket or ring, may be placed around the support body to block channels in the lower assembly that are in communication with the gap in the upper casting assembly. By blocking channels through the support body, a pressure drop adjacent the porous vertical body may be eliminated, thereby inhibiting radial flow through the vertical mold walls.
In pressure casting processes, casting in the radial-only direction may be accomplished, for example, by use of an impermeable casting substrate that blocks flow of the ceramic suspension liquid axially through the casting substrate. Pressure casting in the axial-only direction may be accomplished by blocking radial flow through the mold wall and porous vertical body, for example, by use of a mold with no mold wall openings.
By the processes described herein, a ceramic body may be formed having any shape, such as a large disc-shaped dental milling block suitable for multiple dental components (e.g., 101 mm diameter blocks), or a small milling block suitable for use in milling a single restoration such as a crown.
A solid zirconia disc may be formed by dual-direction vacuum and pressure casting processes that significantly reduce casting time compared to known single direction vacuum casting processes. In one embodiment, a solid zirconia disc having a height greater than or equal to 21 mm may be cast in less than or equal to 2 hours 30 minutes, from a ceramic suspension of micron-sized zirconia particles by processes described herein, wherein the block is cast approximately 12 times as fast as single (axial-only) direction vacuum casting. By processes described herein, solid zirconia discs made from zirconia nano-suspension (e.g., zirconia having a median particle size less than 100 n ay be cast, for example, into a 98 mm diameter block having a cast thickness greater than or equal to 20 mm in 15 days or fewer. Zirconia blocks made from zirconia nano-suspension may be cast that have a thickness greater than 10 mm, or greater than 20 mm, or greater than 30 mm, or greater than 40 mm, in fewer than 15 days. In some embodiments, the cast ceramic blocks made from zirconia nano-suspension may have a fracture toughness value greater than 11 MPa*m1/2.
Zirconia Ceramic Materials
Commercially available yttria-stabilized zirconia powders and commercially available yttria-stabilized zirconia suspensions used to make ceramic casting suspensions are provided in Table 1. In some embodiments, the zirconia ceramic materials were combined to make the zirconia ceramic casting suspensions.
(1) Tosoh Corporation, Tokyo, Japan;
(2) MEL Chemicals Inc., Manchester, England;
(3) Inframat ® Advanced Materials ™, Connecticut, USA.
Micron Suspension: PX-430 (5.5Y) and TZ-3YS (3Y) (Tosoh Corporation, Tokyo, Japan) micron-sized powders were mixed in de-ionized water with addition of Dolapix CE 64 dispersant (Zschimmer & Schwarz, Inc., Lahnstein, Denmark) to make 4.9 mol % Y2O3-stabilized ZrO2 compositional suspension. Mixing was performed by milling in the NETZSCH LabStar (NETZSCH Premier Technologies, LLC. Exton, Pa., USA). The following parameters were used: 500 RPM for pump speed, 2000 RPM for agitator speed. The throughput was 10 kg of 4.9 mol % yttria-containing zirconia suspension.
Zirconia ceramic bodies were cast from commercially available nano-sized yttria-stabilized zirconia suspension, and efficiencies of single (axial) and dual (axial and radial) casting were compared for casting nano-sized zirconia.
A ceramic suspension of nano-size (D50=24 nm) 5 mol % yttria-stabilized zirconia (MELox 5Y) with a solids content of 55 wt % was obtained from Mel Chemicals Inc. (Manchester, England)
The casting apparatus comprised of an upper casting assembly and a lower casting assembly. The upper casting assembly comprised a cylindrical body that was open at top and bottom ends. The top and bottom regions of the cylindrical body were the slurry chamber and the mold, respectively. The slurry chamber was approximately two-thirds the height of the cylindrical body and the mold was approximately one-third of the height of the cylindrical body. The mold cavity of each casting apparatus had a 38 mm diameter. Mold walls were made of an acrylic plastic that was impermeable to the casting suspension liquid during the casting process. For single direction (axial-only) vacuum casting, the vertical mold walls were solid, having no mold wall through holes, thus, preventing radial discharge of suspension liquid from the mold.
For dual direction vacuum casting, the mold wall comprised a plurality of circular 3 mm diameter mold wall openings that were distributed evenly around the mold cavity, except that the bottom perimeter (approximately 8 mm to 10 mm) of the mold wall was solid, having no openings. The openings comprised about 30% of the mold wall surface area. A 20 mm thick porous vertical body comprised of a plaster material covered the outer surface of the mold wall filling the through holes; the plaster in the through holes was level with the inner mold walls forming a smooth cavity surface. An impermeable housing surrounded the mold and porous vertical body, and a gap was formed between the porous vertical body and the impermeable housing for expelling suspension liquid that passed radially through mold wall openings and the porous vertical body during the casting process.
The lower casting assembly comprised a porous support body made from a mixture of plaster of Paris powder and water in the ratio of 100 g and 70 g. The porous casting substrate was formed by making a recess on the upper surface of the porous support body. When assembled, the bottom perimeter of the mold was fitted within the recess of the porous support body. In the dual direction vacuum casting apparatus, the channels around the perimeter of the porous support body aligned with the gap around the perimeter of the porous vertical body of the upper casting assembly. During radial casting, liquid that passed through the mold wall holes and the porous vertical body was evacuated from the casting apparatus through the aligned gap and channels of the upper and lower casting assemblies. For axial casting, liquid that passed axially through the bottom of the mold and into the porous casting substrate, was evacuated through the bottom of the porous support body.
About 280 g of the ceramic suspension was added to each slurry chamber of the single (axial) direction and a dual direction (axial and radial) vacuum casting apparatus. The al level of suspension was marked on the surface of the slurry chamber of each apparatus. A vacuum pressure of about 27 inHg was applied to the bottom surface of the porous supporting body. The suspension was measured daily for 11 days, and the drop in suspension level from the initial mark was recorded.
As reported in Table 2, after vacuum casting for 11 days, the suspension level dropped 85.5 mm under dual directional vacuum casting conditions compared to a 15 mm drop under single directional (axial-only direction) vacuum casting. Thus, over 11 days, the suspension level dropped 5.7 times more in the dual (axial and radial) direction vacuum setup than in the single direction (axial-only) vacuum casting process.
Zirconia ceramic bodies were cast from nano-sized yttria-stabilized zirconia suspensions, and efficiencies of two dual direction vacuum casting apparatus (axial and radial vacuum) having different sized radial through holes were compared for casting nano-sized zirconia.
Two dual direction vacuum casting apparatus were made substantially according to the dual direction apparatus of Example 1. The upper and lower casting assemblies were adapted to accommodate a 101 mm diameter mold, and were modified as described herein. To facilitate radial casting, the first apparatus had multiple 3 mm diameter circular holes through the mold wall; the second casting apparatus had 7 mm diameter circular holes through the mold cavity wall. The mold cavity diameters were 101 mm. A 20 min thick porous vertical body comprised of plaster covered the outer surfaces of the mold walls and covered the holes/openings through the mold wall. An impermeable housing encased the porous vertical body and mold, forming a gap between the impermeable housing and the porous vertical body to evacuate liquid that passed through covered mold wall holes during the casting process. When assembled, gap in the plaster aligned with holes that extended through the thickness of the porous support body.
A 3 mol % yttria-stabilized zirconia nano-suspension having a solid loading of about 55 wt % was obtained from Mel Chemicals. The first casting assembly (with 3 mm holes) was filled with 1800 g of zirconia suspension. The second casting assembly (with 7 mm holes) was also filled with 1800 g zirconia suspension. The initial slurry levels were marked inside of the slurry chambers of each casting assembly. A vacuum pressure of about 27 inHg was maintained through the casting period. Drops in slurry level (measured in mm) and block thickness buildup (mm) were measured daily for 14 days for the first casting assembly (3 mm hole diameter,
As reported in Table 3, and graphically illustrated in
A ceramic body made by dual directional casting of zirconia nano-suspension was tested for fracture toughness.
A 3 mol % yttria-stabilized zirconia nano-suspension having a solid loading of about 55 wt % was obtained from Mel Chemicals. A dual direction (axial and radial) vacuum casting assembly was made substantially according to Example 3, with a mold having a 101 mm diameter cavity and a mold wall with a large rectangular open area (substantially according to
After 19 days of vacuum casting with vacuum pressure of about 27 inHg, a nano-zirconia block 1101 shown in
Samples were prepared from the block for fracture toughness testing which was measured using micro indentation machine (Model HMV-G21, Shimadzu Inc., Maryland, USA). Test specimen prepared from the cast block were sintered at 1150° C. for 2 hours, until approximately full theoretical density was reached. For testing, 19.61 N of load and 15 second dwell time were used. No crack formation was observed adjacent the indentation. The average fracture toughness value was 11.95 MPa·m1/2, as summarized in Table 4. By way of comparison, a pressed micron-sized 3 mol % yttria-stabilized zirconia powder, sintered at 1580° C. to full theoretical density, had an average fracture toughness of 5.01 MPa·m1/2, with crack formation at the tip of indentation.
Zirconia ceramic bodies were cast from suspensions prepared from nano-sized yttria-stabilized zirconia powder. Efficiencies of three casting assemblies having varying mold diameters were compared for casting nano-sized zirconia.
Ceramic suspensions were prepared with 3 mol % and 8 mol % yttria-stabilized zirconia nano-sized powders from Inframat Advanced Materials (CT, USA) to make a 4.9 mol % yttria-stabilized zirconia suspension. The solids loading of the suspensions were approximately 40 wt %, and Dolapix CE 64 dispersant in an amount of about 0.75 wt % to the zirconia mass was added. After all the components were mixed by mechanical mixer, the suspension was aggressively milled in the Netzsch Labstar to yield a suspension with an average particle size of 85 nm.
Casting assemblies were arranged as follows. A first casting assembly was prepared substantially according to Example 2, for a single direction casting (axial only) having a mold with no wall openings and a mold cavity diameter of 38 mm. A second casting assembly was prepared substantially according to Example 1 for dual direction (radial and axial) vacuum casting, wherein the mold wall had 3 mm diameter through holes over about 30% of the cavity mold wall surface area. The mold cavity diameter was 38 mm. A third casting setup was prepared substantially according to Examples 3 through 5, having 3 mm diameter through holes in the mold cavity wall and a cavity diameter of 101 mm.
About 225 g of zirconia ceramic suspension was added to the slurry chambers of the first and second casting assemblies. About 1523 g of the ceramic suspension was added to the slurry chamber of the third casting assembly. The initial levels of suspension were marked on the slurry chamber wall of each setup. The suspensions were cast on porous plaster casting substrates prepared by mixing plaster of Paris powder and water in the ratio of 100 g and 70 g, respectively. A vacuum of about 27 in Hg was maintained during the casting process. The suspension was measured daily for 10 days, and the drop in suspension level from the initial mark was recorded. Table 5 and
After 10 days, for 38 mm diameter bodies, the suspension level dropped by 140 mm in the dual directional casting apparatus (Ex. 7) compared to 66 mm in the single directional casting apparatus (Ex. 6). Thus, the dual directional casting apparatus having a 38 mm diameter mold (Ex. 7) was more than 2 times faster than the single directional casting apparatus, and it was also faster than the dual direction apparatus with the 101 mm diameter mold (Ex. 8). The nano-sized ZrO2 suspensions of Examples 7 and 8, prepared from nano-sized powders that were processed by milling, provided faster casting for dual direction casting than the commercially available nano-sized ZrO2 suspensions of Examples 1, 3 and 4, above.
Zirconia ceramic bodies were cast from commercially available micron-sized yttria-stabilized zirconia. Efficiencies of three casting apparatus were compared for casting micron-sized zirconia.
A single direction (axial) vacuum casting assembly and two dual direction (axial and radial) vacuum casting assemblies having different size holes (diameters of 3 mm and 7 mm), were compared for casting 101 mm diameter ceramic bodies.
A ceramic suspension comprising 4.9 mol % yttria-stabilized zirconia (micron-size) with solid loading of about 72 wt % and Dolapix CE 64 as dispersing agent was prepared. After all components were mixed by using a mechanical mixer, the suspension was aggressively milled in Netzsch Labstar to make homogeneous suspension and to break down agglomerates.
The slurry chambers of the two dual direction vacuum casting setups were each filled with 2500 g of suspension. The single direction (axial) vacuum casting setup was filled with 2400 g of suspension. All three casting setups have mold cavity diameter of 101 mm. Vacuum pressure measuring about 27 inHg was held during the casting process. The initial suspension levels were marked inside of the slurry chambers of all three assemblies. The suspension level drops from the initial marks were measured daily for 5 days, and results are summarized in Table 6 and
Both dual direction vacuum casting assemblies had faster casting rates than the single (axial-only) direction vacuum casting setup. The difference in casting rates between the two dual direction vacuum casting setups was negligible. After 5 days, the suspension level dropped 58 mm in both dual directional casting setups whereas the suspension level dropped 35.5 mm in the single directional casting setup. For micron-sized zirconia ceramic suspensions, casting rates of the dual directional casting setups were 1.6 times faster than the single directional casting setup over 5 days.
Zirconia ceramic bodies were formed from micron-sized yttria-stabilized zirconia ceramic suspension. Efficiencies in single direction (axial) vacuum casting and dual direction vacuum-pressure casting were compared.
A first single-direction apparatus was substantially similar to the apparatus of Example 9, comprising a mold cavity having a 101 mm diameter, wherein the mold walls had no holes or openings through the wall.
A second casting apparatus, suitable for dual direction vacuum-pressure casting, was obtained that was substantially in accordance with Example 3 and 4, except as follows. The walls of the cylinder that comprised the slurry chamber and mold were comprised of 5 mm thick aluminum. The mold cavity diameter was 101 mm, and 3 mm diameter circular openings through the metal mold walls were provided to facilitate radial vacuum. A metal lid was secured to the slurry chamber by screws. In addition to screw holes, the lid had three openings to accommodate a nozzle for delivering the ceramic suspension to the slurry chamber, for introducing air pressure to the slurry chamber, and for a pressure gauge. A porous vertical body surrounded the mold cavity, contacting the metal wall and covering the holes.
A suspension of 4.9 mol % yttria-stabilized zirconia micron-sized zirconia particles was made substantially according to Examples 9-11. 871.5 g of suspension was introduced into the slurry chamber of the first casting apparatus (single direction), and the initial suspension level was marked. The single direction vacuum casting was performed under a vacuum of about 27 inHg, which was applied for 10 hours, over which time the level dropped 13 mm. The weight of the zirconia ceramic that was cast was 513.7 g,
To the second dual direction vacuum-pressure casting setup, 1750 g of suspension was introduced into the slurry chamber and the initial suspension level was marked. The slurry was cast under a pressure of 10 psi (20.4 inHg) and vacuum level of 27 inHg. After 10 hours, the ceramic suspension level dropped 31 mm. The weight of the dried cast body was 1012 g.
Zirconia ceramic bodies were cast from a suspension in an adaptable dual-direction, vacuum-pressure casting apparatus, operated under different casting conditions.
An adaptable casting apparatus was made as follows. An upper casting assembly comprised a metal cylinder having top and bottom regions comprising a slurry chamber and a mold, and a metal ring separating the slurry chamber and mold cavity. The mold cavity diameter was 101 mm, and to facilitate radial vacuum, the mold wall had a large open area substantially similar to
The outer surface of the mold was covered by a plaster, porous vertical body that covered the open area of the mold wall, and vertical channels were made in the porous vertical body. The mold and porous vertical body were surrounded by an impermeable case. A metal lid was secured to the top of the slurry chamber by screws. The lid had three openings that accommodated a nozzle to deliver the ceramic suspension into the slurry chamber, for introducing air pressure into the slurry chamber, and for a pressure gauge. The upper casting assembly was engaged with a lower casting assembly substantially as described in Example 1, and adapted for use with a 101 mm diameter mold.
Radial-only direction vacuum casting was achieve by placing an impermeable casting substrate over the porous support body, blocking vacuum in the axial direction and preventing flow of suspension liquid through the bottom of the mold. Axial-only direction vacuum casting was achieved by placing an impermeable rubber gasket around the bottom perimeter of the porous support body to block vacuum through the channels preventing pressure drop adjacent the porous vertical body.
To compare the efficiencies of different casting operations, the dual direction vacuum-pressure casting setup was operated at different conditions, and the results are summarized at Table 7. A suspension of micron sized 4.9 mol % yttria-stabilized ZrO2, prepared according to Examples 9 through 11, was used to cast ZrO2. Zirconia disc blocks were formed in a mold having a mold diameter of 101 mm and mold thickness of 21 mm. The weight and volume of cast blocks were measured. The percentage of cast zirconia was calculated for each block after comparing the volume of the mold cavity and volume of the ZrO2 cast.
The average intensity of vacuum during casting was about 27 inHg. After casting for 3 hours under vacuum without application of pressure, the volume percentages (based on the volume of the mold cavity) of cast zirconia suspension was 24% for application of vacuum in the radial direction, 40% for vacuum in the axial direction, and 52% for application of vacuum in both axial and radial directions.
With application of axial vacuum and radial vacuum of 27 inHg, after three hours, the volume percentage (based on the volume of the mold cavity) of cast zirconia was 52% with no application of pressure, 80% with the application of 40 psi, 89% with the application of 60 psi, and 97% with the application of 80 psi.
With application of axial vacuum and radial vacuum of about 27 inHg and application of 40 psi pressure through the slurry chamber, the volume percentage of ZrO2 cast was 80% after casting for 3 hours, 97% after casting for 4 hours, and 98% after casting for 5 hours.
This application claims the benefit of, and priority to, U.S. Provisional Patent Application No. 62/967,192, filed Jan. 29, 2020. The entirety of the foregoing application is incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 399064 | McLean | Mar 1889 | A |
| 3111396 | Ball | Nov 1963 | A |
| 3523916 | Needham et al. | Aug 1970 | A |
| 3837825 | Loxley et al. | Sep 1974 | A |
| 4431420 | Adair | Feb 1984 | A |
| 4556530 | van der Scheer | Dec 1985 | A |
| 4769349 | Hillig et al. | Sep 1988 | A |
| 4772436 | Tyszblat | Sep 1988 | A |
| 4828495 | Bell et al. | May 1989 | A |
| 4906424 | Hughes et al. | Mar 1990 | A |
| 4983182 | Kijima et al. | Jan 1991 | A |
| 5156856 | Iwasaki | Oct 1992 | A |
| 5185177 | Kijima et al. | Feb 1993 | A |
| 5192325 | Kijima et al. | Mar 1993 | A |
| 5203936 | Dolhert et al. | Apr 1993 | A |
| 5256609 | Dolhert | Oct 1993 | A |
| 5296175 | Iwaski et al. | Mar 1994 | A |
| 5342564 | Wei et al. | Aug 1994 | A |
| 5372178 | Clarr et al. | Dec 1994 | A |
| 5395437 | Chiou | Mar 1995 | A |
| 5441408 | Moschik | Aug 1995 | A |
| 5443770 | Krstic et al. | Aug 1995 | A |
| 5660863 | Nakano | Aug 1997 | A |
| 5672055 | Koutavas | Sep 1997 | A |
| 5776382 | Kim et al. | Jul 1998 | A |
| 5785911 | Willkens et al. | Jul 1998 | A |
| 5788891 | Gauckler et al. | Aug 1998 | A |
| 5843348 | Giordano | Dec 1998 | A |
| 5849068 | Hofmann, geb. Roth et al. | Dec 1998 | A |
| 5975905 | Kim et al. | Nov 1999 | A |
| 6007926 | Provenzano et al. | Dec 1999 | A |
| 6180034 | Buck et al. | Jan 2001 | B1 |
| 6200526 | Fox et al. | Mar 2001 | B1 |
| 6291378 | Evans et al. | Sep 2001 | B1 |
| 6431800 | Suzuki | Aug 2002 | B1 |
| 6814917 | Watanabe et al. | Nov 2004 | B1 |
| 6878456 | Castro et al. | Apr 2005 | B2 |
| 6896846 | Varma et al. | May 2005 | B1 |
| 6946013 | Alward et al. | Sep 2005 | B2 |
| 7271100 | Lee et al. | Sep 2007 | B2 |
| 7655586 | Brodkin et al. | Feb 2010 | B1 |
| 8178012 | Khan et al. | May 2012 | B1 |
| 8196755 | Diefenbacher et al. | Jun 2012 | B2 |
| 8268230 | Cherepy et al. | Sep 2012 | B2 |
| 8572484 | Maruyama et al. | Oct 2013 | B2 |
| 8785518 | Suh et al. | Jul 2014 | B2 |
| 8813364 | Schechner et al. | Aug 2014 | B2 |
| 9039947 | Jahns et al. | May 2015 | B2 |
| 9193630 | Bocciarelli et al. | Nov 2015 | B2 |
| 9309155 | Nahas | Apr 2016 | B2 |
| 9434651 | Carden | Sep 2016 | B2 |
| 9790125 | Beall et al. | Oct 2017 | B2 |
| 9790129 | Carden | Oct 2017 | B2 |
| 9925126 | Kolb et al. | Mar 2018 | B2 |
| 20010048969 | Constantino et al. | Dec 2001 | A1 |
| 20020037800 | Yang | Mar 2002 | A1 |
| 20020155412 | Panzera et al. | Oct 2002 | A1 |
| 20030096214 | Luthardt et al. | May 2003 | A1 |
| 20040119180 | Frank et al. | Jun 2004 | A1 |
| 20050023710 | Brodkin et al. | Feb 2005 | A1 |
| 20050203231 | Halpert et al. | Sep 2005 | A1 |
| 20060014390 | Lee et al. | Jan 2006 | A1 |
| 20070056467 | Panzera | Mar 2007 | A1 |
| 20070134496 | Katagiri et al. | Jun 2007 | A1 |
| 20080085828 | Khan et al. | Apr 2008 | A1 |
| 20080164402 | Menke et al. | Jul 2008 | A1 |
| 20080258358 | Oswald et al. | Oct 2008 | A1 |
| 20090098365 | Moeltgen | Apr 2009 | A1 |
| 20090115084 | Moon | May 2009 | A1 |
| 20090220787 | Granger et al. | Sep 2009 | A1 |
| 20090291011 | Zhang et al. | Nov 2009 | A1 |
| 20090321971 | Brodkin et al. | Dec 2009 | A1 |
| 20100003157 | Scholl et al. | Jan 2010 | A1 |
| 20100249305 | Laubersheimer et al. | Sep 2010 | A1 |
| 20110236860 | Jahns et al. | Sep 2011 | A1 |
| 20110260349 | Rolf et al. | Oct 2011 | A1 |
| 20120193823 | Goetzinger et al. | Aug 2012 | A1 |
| 20130224454 | Jung et al. | Aug 2013 | A1 |
| 20130224688 | Mayr et al. | Aug 2013 | A1 |
| 20130313738 | Carden | Nov 2013 | A1 |
| 20130341812 | Schechner et al. | Dec 2013 | A1 |
| 20140008826 | Dierkes et al. | Jan 2014 | A1 |
| 20180170812 | Xu et al. | Jun 2018 | A1 |
| Number | Date | Country |
|---|---|---|
| 1215711 | Aug 2005 | CN |
| 1236761 | Jan 2006 | CN |
| 1471423 | Jul 1963 | DE |
| 0329284 | Aug 1989 | EP |
| 0587160 | Mar 1994 | EP |
| 411019910 | Jan 1999 | JP |
| 2006024098 | Mar 2006 | WO |
| 2007000310 | Jan 2007 | WO |
| 2009061410 | May 2009 | WO |
| 2013181018 | Dec 2013 | WO |
| Entry |
|---|
| Written opinion of the International Searching Authority for PCT/US2008/012489, dated Dec. 31, 2008, in 4 pages. |
| International Search report in International Application No. PCT/US2013/041941 dated Oct. 24, 2013. |
| U.S.P.T.O Non-final Office Action issued in U.S. Appl. No. 12/290,089 dated Jun. 2, 2009. |
| U.S.P.T.O Non-final Office Action issued in U.S. Appl. No. 12/290,089 dated Dec. 1, 2009. |
| International Search Report issued in Application No. PCTUS2008/12489 dated Dec. 31, 2008. |
| Non-Final Office Action issued in U.S. Appl. No. 13/481,810 dated Jan. 15, 2016. |
| Final Office Action issued in U.S. Appl. No. 13/481,810 dated Sep. 22, 2015. |
| Non-Final Office Action issued in U.S. Appl. No. 13/481,810 dated Mar. 12, 2015. |
| Non-Final Office Action issued in U.S. Appl. No. 13/481,810 dated Aug. 22, 2014. |
| International Supplementary Search Report issued for PCT/US2008/012489, dated Feb. 16, 2018, in 10 pages. |
| Number | Date | Country | |
|---|---|---|---|
| 20210229314 A1 | Jul 2021 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62967192 | Jan 2020 | US |
