Source: http://www.google.com/patents/US7905951?ie=ISO-8859-1&dq=%22Meaning-based+information+organization+and+retrieval%22
Timestamp: 2014-03-11 18:47:37
Document Index: 581984427

Matched Legal Cases: ['Application No. 04', 'Application No. 00', 'Application No. 01', 'Application No. 01', 'Application No. 03759353', 'Application No. 03759353', 'Application No. 03759353', 'Application No. 03759353', 'Application No. 04', 'Application No. 05024830', 'Application No. 05024830', 'Application No. 2', 'Application No. 01927008', 'Application No. 04001558', 'Application No. 04001558', 'Application No. 04752633', 'Application No. 2000', 'Application No. 2000', 'Application No. 2001', 'Application No. 2004', 'Application No. 2006', 'Application No. 549079', 'Application No. 549079', 'Application No. 200480018360']

Patent US7905951 - Three dimensional printing material system and method using peroxide cure - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA materials system and methods are provided to enable the formation of articles by Three Dimensional Printing. The materials system includes a transition metal catalyst that facilitates the reaction of an acrylate-containing binder with a particulate material....http://www.google.com/patents/US7905951?utm_source=gb-gplus-sharePatent US7905951 - Three dimensional printing material system and method using peroxide cureAdvanced Patent SearchPublication numberUS7905951 B2Publication typeGrantApplication numberUS 11/952,727Publication dateMar 15, 2011Filing dateDec 7, 2007Priority dateDec 8, 2006Also published asCN101568422A, CN101568422B, EP2089215A2, EP2664442A1, US8157908, US20080138515, US20110130489, WO2008073297A2, WO2008073297A3Publication number11952727, 952727, US 7905951 B2, US 7905951B2, US-B2-7905951, US7905951 B2, US7905951B2InventorsDerek X. WilliamsOriginal AssigneeZ CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (100), Non-Patent Citations (67), Referenced by (1), Classifications (7), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetThree dimensional printing material system and method using peroxide cureUS 7905951 B2Abstract A materials system and methods are provided to enable the formation of articles by Three Dimensional Printing. The materials system includes a transition metal catalyst that facilitates the reaction of an acrylate-containing binder with a particulate material.
10. The kit of claim 1, wherein an internal angle of friction of the particulate material has a value ranging from 40� to 70�.
RELATED APPLICATION This application claims priority to U.S. Provisional Patent Application Ser. No. 60/873,730, filed Dec. 8, 2006, the disclosure of which is hereby incorporated by reference in its entirety.
TECHNICAL FIELD This invention relates generally to rapid prototyping techniques and, more particularly, to a three-dimensional printing material and method using a peroxide cure.
Two well-known methods for rapid prototyping include a selective laser sintering process and a liquid binder Three Dimensional Printing process. These techniques are similar, to the extent that they both use layering techniques to build three-dimensional articles. Both methods form successive thin cross-sections of the desired article. The individual cross-sections are formed by bonding together adjacent grains of a granular, (i.e., particulate) material on a generally planar surface of a bed of the granular material. Each layer is bonded to a previously formed layer at the same time as the grains of each layer are bonded together to form the desired three-dimensional article. The laser-sintering and liquid binder techniques are advantageous because they create parts directly from computer-generated design data and can produce parts having complex geometries. Moreover, Three Dimensional Printing may be quicker and less expensive than machining of prototype parts or production of cast or molded parts by conventional �hard� or �soft� tooling techniques that can take from a few weeks to several months, depending on the complexity of the item.
SUMMARY OF THE INVENTION In an embodiment of the invention, strong parts may be made by Three Dimensional Printing over particulate material build material without a need for infiltration. Typical existing printing processes include a post-processing infiltration step to increase the strength of the printed article. Articles printed with the peroxide-containing binders described herein have strengths comparable to that of infiltrated articles, e.g., about 20 MPa, thereby eliminating a need for the infiltration step.
One or more of the following features may be included. The particulate material may possess an internal angle of friction greater than 40� and less than 70�. The particulate material possess a critical surface tension greater than 20 dynes/cm. The particulate material may include about 50%-90% by weight of the insoluble filler, about 10-50% by weight of the soluble filler, and about 0.01-0.5% by weight of the transition metal catalyst.
One or more of the following features may be included. The fluid binder may have a contact angle of less than 25� on the particulate material. The fluid binder may include about 40%-95% by weight of the (meth)acrylate monomer, about 5-25% by weight of the allyl ether functional monomer/oligomer, and about 0.5-5% by weight of the organic hydroperoxide. The fluid binder may also include 0-1% by weight of surfactant. The fluid binder may include a (meth)acrylate oligomer, e.g., about 10-40% by weight of the (meth)acrylate oligomer. The fluid binder may include a first accelerator, e.g., up to about 2% by weight of the first accelerator. The first accelerator may include dimethylacetoacetamide.
FIG. 18 c is a CAD drawing of the part portion printed in FIGS. 18 a and 18 b. DETAILED DESCRIPTION Three Dimensional Printing Referring to FIG. 1, in accordance with a printing method using the materials system of the present invention, a layer or film of a particulate material 20, i.e., an essentially dry, and free-flowing powder, is applied on a linearly movable surface 22 of a container 24. The layer or film of particulate material 20 may be formed in any suitable manner, for example using a counter-roller. The particulate material 20 applied to the surface includes an insoluble filler material, a soluble filler material, and a transition metal catalyst. The particulate material 20 may also include a pigment and/or a processing aid material.
The first portion 30 of the particulate material activates the fluid binder 26, causing the fluid binder to initiate polymerization into a solid that adheres together the particulate mixture to form a conglomerate of the particulate material 20 (powder) and fluid binder 26. The conglomerate defines an essentially solid circular layer that becomes a cross-sectional portion of an intermediate article 38 (see, e.g., FIGS. 3 and 4). As used herein, �activates� is meant to define a change in state in the fluid binder 26 from essentially stable to reactive. This definition encompasses the decomposition of the organic hydroperoxide in the fluid binder 26 once in contact with the transition metal in the particulate material 20. When the fluid initially comes into contact with the particulate mixture, it immediately flows outwardly (on a microscopic scale) from the point of impact by capillary suction, dissolving the soluble filler within a time period, such as 30 seconds to one minute. A typical droplet of fluid binder has a volume of about 50 picoliters (pl), and spreads to a diameter of about 100 micrometer (μm) after coming into contact with the particulate mixture. As the fluid binder dissolves the soluble filler, the fluid viscosity increases dramatically, arresting further migration of the fluid from the initial point of impact. Within a few minutes, the fluid with soluble filler dissolved therein flows and adheres to the insoluble filler, forming adhesive bonds between the insoluble filler particulate material. The fluid binder is capable of bonding together an amount of the particulate mixture that is several times the mass of a droplet of the fluid. As the reactive monomers/oligomer of the fluid binder polymerize, the adhesive bonds harden, joining the insoluble filler particulate material and, optionally, pigment into a rigid structure, which becomes a cross-sectional portion of the final article 40.
The contact angle, θ, is the angle of contact between a liquid and solid. A contact angle of 0� suggest that the fluid will spontaneously wet the entire surface of the solid to which it is applied, while a contact angle greater than 90� suggests that the fluid will not spontaneously spread and wet the surface of the solid to which it is applied. Spontaneously used herein is in reference to thermodynamic equilibrium, and does not denote an instance of time. The contact angle may be defined by the Young and Dupr� equation:
cos ⁢ ⁢ θ = γ sv - γ sl γ lv Equation ⁢ ⁢ 2 where γsv, is the surface energy at the solid and vapor interface, and γsl is the surface energy at the solid and liquid interface. The difference of γsv-γsl in the numerator of Equation 2 may be defined as the adhesion tension of the solid at the solid-liquid-vapor interfaces. It may be desirable to have this adhesion tension greater than or equal to the surface tension of the fluid at the liquid-vapor interface. The adhesion tension may be related to the surface characteristic defined as the critical surface tension by Zisman, which is described in the following paragraphs.
cos ⁢ ⁢ θ = m 2 t ⁢ η ρ 2 ⁢ σ ⁢ ⁢ c Equation ⁢ ⁢ 3 where θ is the contact angle at the liquid-solid interface, m is the mass of fluid, t is time, η is the viscosity of the fluid, ρ is the density of the fluid, and c is a material constant.
The material constant c may be determined by infiltrating a porous medium with a very low surface tension fluid that will have a contact angle of 0� against the solid surface of particles comprising the porous medium. n-Hexane is a common fluid used for such purposes, having a surface tension of 18 dynes/cm; it is assumed to have a contact angle of 0� against most solid surfaces. This makes the value of cos θ equal to 1 in Equation 3, thereby making it possible to solve for the material constant c since the fluid properties of n-hexane are known. This leaves one to measure the rate of mass increase of the fluid infiltrating the porous medium over time. This mass-time response may be measured by use of a Kr�ss Processor Tensiometer K100 with accessories for Washburn contact angle measurement, available from KRUSS USA based in Mathews, N.C., or by use of a KSV Sigma 70 Tensiometer from KSV Instruments USA based in Monroe, Conn. With these instruments, a vial of powder is prepared. The vial is perforated at a bottom portion, with a piece of porous filter paper preventing the powder from pouring through the perforated bottom. The vial filled with powder is attached to a microbalance, and the bottom of the vial is brought into contact to the surface of the fluid, in this case n-hexane. Software records the mass increase of the vial over time from the microbalance as the fluid is drawn into the powder in the vial largely by capillary pressure. One may then plot the mass squared over time, which should result in a straight line during the time fluid is infiltrating into the powder in the vial (see FIG. 5, that illustrates a typical response from the Washburn infiltration method to determine the material constant and contact angle of a fluid against a particulate material). The slope may be calculated from that plot, which corresponds to the value of m2/t in Equation 3. After the slope is calculated, one may solve for the material constant c.
c = 1 2 ⁢ π 2 ⁢ r 5 ⁢ n 2 Equation ⁢ ⁢ 4 where r is the average capillary radius of the porous medium, and n is the number of capillary channels. Loosely packed powder will have a larger average capillary radius increasing the material constant, and, conversely, densely packed powder will have smaller average capillary radius decreasing the material constant.
16.0 cP @ 21� C.
The concepts presented here regarding contact angle, capillary pressure, and adhesion tension may be found in the Physical Chemistry of Surfaces, Adamson, Arthur W., Interscience Publishers, Inc., 1967, and regarding the Washburn method in �Wettability Studies for Porous Solids Including Powders and Fibrous Materials�Technical Note #302� by Rulison, Christopher, 1996, which is a manufacturer's application note from KRUSS USA, the disclosures of which are incorporated herein by reference in their entireties.
The flexural test bars were printed on a Spectrum Z� 510 Three Dimensional Printer available from Z Corporation in Burlington, Mass. modified to use a SM-128 piezoelectric jetting assembly along with an Apollo II Printhead Support Kit both available from FUJIFILM Dimatix based in Santa Clara, Calif. The flexural test bars were printed applying the fluid binder listed on Table 5 through the SM-128 jetting assembly over the particulate material at a layer thickness of 100 microns. The fluid was deposited selectively and uniformly at each layer to occupy 32% by volume of the flexural test part. The flexural test parts were allowed to solidify for 1 hour before they were extracted from the build bed of the Spectrum Z510 and placed in a 60� C. oven for 12 hours to cure. Table 6 summarizes flexural properties of the particulate material compositions that were measured. Referring to FIG. 7, a graphical representation of the results collected is provided. The results suggest that soluble fillers with molecular weights less than 100,000 g/mol exhibit lower flexural properties than soluble fillers with molecular weights greater than 100,000 g/mol.
The effect of the surfactant increasing the surface energy of the particulate material may be measured using the Washburn method describe earlier by infiltrating a particulate material formulation with a series of liquid solutions with varying surface tension values. The contact angles, θ, are determined for each surface tension. Then the cos θ values are plotted against the surface tension values to construct a Zisman plot. The data are used to linearly extrapolate a trend line to the value where cos θ equals 1 (when θ=0�) to determine the critical surface tension of the particulate material which was described earlier to be related to the adhesion tension of the solid at the solid-liquid-vapor interfaces. This test was performed on the formulations listed in Table 7. See FIG. 8 (particulate material with paraffinic oil processing aid) and 9 (particulate material with a paraffinic oil and surfactant blend processing aid).
Further discussion regarding critical surface tension may be found in Physical Chemistry of Surfaces, Adamson, Arthur W., Interscience Publishers, Inc., 1967, and regarding the Washburn method in �Wettability Studies for Porous Solids Including Powders and Fibrous Materials�Technical Note #302� by Rulison, Christopher, 1996, which is a manufacturer's application note from KRUSS USA; these disclosures are incorporated herein by reference in their entireties.
The surfactant is a preferred additive in the formulation of the fluid binders used in Three Dimensional Printing to reduce the surface tension of the binder so that the surface tension is equal to or less than the critical surface tension of the particulate material, such that the contact angle of the fluid binder against the particulate material is less than 25�, but preferably closer to if not equal to 0�. This allows the fluid binder to wet out onto the particulate material without creating large capillary forces that may cause (i) fissuring at points where the printed area on the particulate material splits apart and (ii) balling where the fluid binder sits on the surface of the particulate material. Both of these occurrences may cause surface defects on the bottoms of flat surfaces of printed articles.
Referring to FIGS. 10 a and 10 b, the effect of the fluid binder formulation is illustrated by laser profilometer scans of flat bottom surfaces of articles at 50 micron resolution on the x and y axes. FIG. 10 a illustrates an example of good wetting behavior with contact angles less than 25� when the binder has a surface tension at or below a critical surface tension of the particulate material and wets smoothly over the particulate material. For example, the critical surface tension of the particulate material may be greater than 20 dynes/cm. FIG. 10 b illustrates an example of poor wetting behavior with contact angles greater than 25� when the binder has a surface tension greater than the critical surface tension of the particulate material causing the binder to wet irregularly over the particulate material and creating fissures.
Fluid formulations of various embodiments of the instant invention are somewhat similar to anaerobic adhesive formulations commonly known as �threadlockers� such as LOCTITE 290 from Loctite based in Rocky Hill, Conn. and which is disclosed by Krieble in U.S. Pat. No. 2,895,950 assigned in 1957 to American Sealants Company based in Hartford, Conn., incorporated herein by reference in its entirety. Aerobically curing formulations using allyl ethers are also known to the art, as described by Cantor et al. in U.S. Pat. No. 5,703,138 assigned to Dymax Corporation, incorporated herein by reference in its entirety. FUJIFILM Dimatix based in Santa Clara, Calif. has a published application note describing the application of LOCTITE 290 adhesive through one of their piezo jetting assemblies to accurately deliver adhesive to a substrate. However, these formulations do not include a surfactant. The fluid adhesive products described in these references do not have the proper surface tension requirements needed for proper wetting, if they were applied onto the particulate material as described in various embodiments of the instant invention. These materials are not intentionally designed to have a surface tension lower than that of the substrate to which they are to be applied, thereby achieving a contact angle of less than 25 degrees. This can be demonstrated by using the Washburn method with the following particulate formulation (Table 8) and binder formulations (Tables 9 and 10).
Referring to Table 11, the high contact angle LOCTITE 290 has on the particulate material formulation indicates that this product would not wet out properly onto the particulate material when applied during Three Dimensional Printing, and would create articles with rough, irregular bottom surfaces, having defects similar to the defects illustrated in FIG. 10 b. A fluid binder properly formulated to have a surface tension lowered to at least 25 dynes/cm so that it has a contact angle less than 25� and close to, if not equal to 0� will wet out the powder properly, resulting in a smooth bottom facing surface with less edge curling distortion, as is exhibited in FIG. 10 a. Surfactants may be used in photocurable inkjet fluid formulation, as disclosed, for example, in U.S. Pat. No. 6,433,038 to Tanabe, where surfactants are used to stabilize dyes and pigments in the disclosed fluid inkjet formulation. Huo et al., in an international patent application PCT/US2005/025074 disclose the use of surfactants to improve wettability of the fluid over non-porous plastic substrates and to control the dynamic surface tension of the fluid for faster meniscus reformation at the nozzle of a DOD device during jetting. These formulations do not use surfactants to decrease the capillary pressure exerted by the fluid when applied on a particulate material, as disclosed herein.
Another exemplary formulation listed on Table 12 shows a particulate powder formulation with a lower critical surface tension than critical surface tensions of particulate formulations disclosed on Table 7. See FIG. 11, which is a Zisman plot of a particulate material including a tackifier processing aid. The surface tension of the fluid binder is essentially at the critical surface tension of the particulate material, and therefore results in a contact angle equal to 0�. The contact angle may be greater than 0� and possibly less than 25� if the critical surface tension is 2 dynes/cm less than the surface tension of the binder. This upper limit of a contact angle is estimated from Equation 2 by dividing the critical surface tension of the solid by the surface tension of the fluid. The contact angle of the fluid binder against both of the particular material listed in Table 12 was determined from the Washburn method to have an average cos θ value of 1.02+/−0.05 at 99% confidence, which would result in a contact angle between 0� and 14� within the 99% confidence interval range of the cos θ value. This fluid binder, when applied to the particulate material disclosed in Table 12, results in proper wetting of the fluid binder over the particulate material to impart a smooth bottom finish, as illustrated in FIG. 10 a.
TABLE 12 Particulate Material Ingredients % by wt. Fliud Binder Ingredients % by wt MOSCI GL0179 glass 84.58% Sartomer SR-423A Isobornyl Acrylate 20.00% microspheres Elvacite 2014 15.20% Sartomer SR-209 Tetraethylene glycol 67.5% dimethacrylate Regalrez 1094 0.10% Sartomer CN9101 Allylic Oligomer 10.00% Light Mineral Oil 0.07% di-tert-butyl hydroquinone 0.05% Tergitol 15-S-5 0.01% BYK UV 3500 surfactant 0.05% Cobalt Octoate, 65% 0.04% Luperox CU90 2.4% in mineral spirits Physical Properties Zisman's Critical 24+/2 dynes/cm at Viscosity 17.5 cP @ 24� C. Surface Tension 99.5% confidenece Surface Tension 23.733 dynes/cm Density 1.004 g/cc Kit
The fluid binder may have a contact angle of less than 25� on the particulate material. In an embodiment, the fluid binder may include about 40%-95% by weight of the (meth)acrylate monomer, about 5-25% by weight of the allyl ether functional monomer/oligomer, and about 0.5-5% by weight of the organic hydroperoxide. The fluid binder may also include 0%-1% by weight of surfactant. The fluid binder may include a (meth)acrylate oligomer, e.g., about 10-40% by weight of the (meth)acrylate oligomer. The fluid binder may also include a first accelerator such as dimethylacetoacetamide, e.g., up to about 2% by weight of the first accelerator.
In embodiments of the current invention employing a peroxide cure process, a user typically waits the above-indicated time after the article is printed before removing the article from the printer. The article may be heated to a range of about 40� C. to about 100� C. to accelerate the aerobic cure at the surface of the article. Heat may be supplied through convection, conduction, infra-red radiation, microwave radiation, radio-wave radiation, or any other suitable method.
TABLE 14 % by wt. % by wt. % by wt. Fluid Binder Ingredients 1 2 3 Sartomer SR209 Tetraethylene 57.50% 57.45% 69% glycol dimethacrylate Sartomer SR-506 Isobornyl 30.00% 30.00% 29% methacrylate Sartomer CN-9101 allylic 10.00% 10.00% � oligomer Sigma-Aldrich di-tert-butyl- 0.05% 0.05% � hydroquinone Sigma-Aldrich hydroquinone � 0.05% � BYK UV3500 Surfactant 0.05% 0.05% � Arkema Luperox CU90 2.40% 2.40% � cumene hydroperoxide CIBA Irgacure 819 � � 2% Mixtures, listed in Table 15, totaling 24 to 26 grams were prepared and placed in a polypropylene dish 40 mm in diameter and 11 mm deep; enough of each of the mixture was used to completely fill the polypropylene dish; usually about 18 to 20 grams.
One can see that the photocurable example exhibits a hardness development rate on the order of 1000� greater than the current embodiment. This hardness rate is related to the rate of conversion of double bonds on the (meth)acrylate monomer. The conversion of the carbon-to-carbon double bonds into single carbon-to-carbon bonds with other monomers decreases the amount of free volume in the fluid binder as it polymerizes. The instantaneous conversion of monomers into a polymer in a photocurable fluid binder causes an instantaneous shrinkage upon exposure to ultraviolet light, which forces selectively printed areas to curl and warp out of the plane of the build bed, causing the selectively printed areas to be dragged and displaced as successive layers are spread. The slower hardening rate of some embodiments relates to a slower conversion rate and where selectively printed areas do not exhibit the immediate distortion of curling and warping out of the plane of the build bed to successively print layer upon layer without dragging or displacement of features on an article. Preferably, the 1 mm penetration hardening rate is between 0.01/minute and 1.0/minute.
Co+2+ROOH→Co+3+RO.+OH− The oxidized Co+3 ion can then be reduced to Co+2 via
Co+3+ROOH →Co+2+ROO.+H+ and/orCo+3+OH−→Co+2+.OH
Background information regarding the decomposition mechanisms of hydroperoxides using cobalt may be found in the Handbook of Adhesive Technology, Pizzi, A. and Mittal, K. L., Marcel Dekker, Inc., 2003, and regarding the mechanism of allyllic polymerization in �Polyallyl Glycidyl Ether Resins for Very Fast Curing High Performance Coatings,� presented by Knapczyk, J. at the 65th Annual Meeting of the Federation of Societies for Coatings Technology, in Dallas, Tex., on Oct. 6, 1987, the disclosures of these references are incorporated herein by reference in their entireties.
Compositions have been disclosed that relate to control of the flow properties of the build material in Three Dimensional Printers. The three principal methods are the addition of liquid �processing aids,� control of grain size distribution, and the addition of solid fillers that contribute to the frictional behavior of the build material. Many candidate materials have been disclosed previously, for example, in U.S. Patent Publication Number 2005/0003189, the disclosure of which is incorporated herein by reference in its entirety. Some mechanical properties of dry particulate build materials are disclosed in the following discussion that are particularly suited for use in Three Dimensional Printing, especially in contrast to other formulations of similar materials for other uses that do not require special flow characteristics of the raw materials.
ϕ = s r � 180 π Equation ⁢ ⁢ 6 where r would equal the outside radius of the drum. The angle, φ, is the internal angle of friction that particulate material has under these particular test conditions at a room temperature between 65 to 75� F. Various particulate materials known to have good and bad spreading characteristics are compared using this test method, and desirable range of internal angles of friction were determined. Table 18 summarizes the particulate material compositions that were measured. Referring to FIG. 16, a graphical representation of the results collected is provided.
TABLE 18 Particulate Material Compositions % by wt Ingredients A B C D E F G H I Potter's 84.64% 79.72% 100% 99.8% Spheriglass 2530 CP03 MoSci GL0179 84.58% Zinc Oxide 4.75% Pigment Lucite Elvacite 15.00% 15.20% 15.19% 2014 Eastman Regalrez 0.10% 1094 Mineral Oil 0.19% 0.07% 0.18% 0.2% DOW Tergitol 0.01% 15-S-5 Cobalt Octoate, 0.17% 0.04% 0.16% 65% in Mineral Spirits Z Corporation 100% zp102 Z Corporation 100% zp100 Z Corporation 100% zp130 Z Corporation 100% ZCast 501 Internal Angle of 77� +/− 3� 64� +/− 3� 36� +/− 3� 53� +/− 12� 59� +/− 13� 32� +/− 3� 81� +/− 9� 48� +/− 5� 55� +/− 11� Friction +/− 95% Confidence Interval Three Too Good Too Good Good Too Too Good Good Dimensional Cohesive Flowable Flowable Cohesive Printing suitability Based on the results indicated in Table 18 and illustrated in FIG. 16, one can conclude that powders that have an internal angle of friction greater than 40� and less than 70� are suitable for Three Dimensional Printing.
FIGS. 17 a and 17 b compare surface finish scans from a VIKING laser profilometer from Solarius. As one may expect, a particulate material with an internal angle of friction that is between 40� and 70� (FIG. 17 a) provides a smoother finish than a particulate material with an internal angle of friction greater than 70� (FIG. 17 b) where the powder is too cohesive to spread an even layer of particulate material, resulting in an article that has very rough and uneven surface finish. FIG. 17 c is a CAD drawing of the formed part illustrated in FIGS. 17 a and 17 b. FIGS. 18 a and 18 b compare surface finish scans from a VIKING laser profilometer from Solarius. As one may expect, a particulate material with an internal angle of friction that is between 40� and 70� (FIG. 18 a) provides a smoother finish than a particulate material with an internal angle of friction less than 40� (FIG. 18 b) where the powder is too flowable and unable to resist the spreading forces causing previous printed layers to be displaced, resulting in an article that has a rough and uneven surface finish, or even artifacts missing from the surface of the article because they were displaced. FIG. 18 c is a CAD drawing of the formed part illustrated in FIGS. 18 a and 18 b. This test is a fairly useful technique for identifying relative performance properties between different candidate materials. The preferred method for evaluating flow properties of candidate build materials during formal optimization after the initial selection period is to test samples of the material on a working three dimensional printer. Certain pathological geometries are known to those experienced in the art, and they can be evaluated either qualitatively or quantitatively. One particularly useful part for observing stability during spreading is a flat plate studded with pegs that are oriented downward during the build. During printing, the earliest layers addressed are a series of disconnected patches that are relatively free to shift in the build material. After these have been formed, a plate is printed that joins all of the pegs together in a single object. One can easily examine whether the pegs are uniform and straight, and one can evaluate the quality of spreading on that basis.
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Du Pont De Nemours And CompanySolid imaging method using photohardenable compositions containing hollow spheresUS5053090Jul 2, 1990Oct 1, 1991Board Of Regents, The University Of Texas SystemSelective laser sintering with assisted powder handlingUS5058988Nov 8, 1988Oct 22, 19913D Systems, Inc.Apparatus and method for profiling a beamUS5059021Nov 8, 1988Oct 22, 19913D Systems, Inc.Apparatus and method for correcting for drift in production of objects by stereolithographyUS5059266May 23, 1990Oct 22, 1991Brother Kogyo Kabushiki KaishaApparatus and method for forming three-dimensional articleUS5059359Apr 18, 1988Oct 22, 19913 D Systems, Inc.Methods and apparatus for production of three-dimensional objects by stereolithographyUS5071337Feb 15, 1990Dec 10, 1991Quadrax CorporationApparatus for forming a solid three-dimensional article from a liquid mediumUS5071503Oct 16, 1989Dec 10, 1991N.C.T. 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Dupont De Nemours And CompanyMethod and apparatus for fabricating three dimensional objects from photoformed precursor sheetsUS5096491Jul 16, 1990Mar 17, 1992Honshu Paper Co., Ltd.Aqueous starch slurry adhesiveUS5096530Jun 28, 1990Mar 17, 19923D Systems, Inc.Resin film recoating method and apparatusUS5104592Apr 17, 1989Apr 14, 19923D Systems, Inc.Method of and apparatus for production of three-dimensional objects by stereolithography with reduced curlUS5106288Apr 11, 1989Apr 21, 1992Austral Asian Lasers Pty Ltd.Laser based plastic model making workstationUS5121329Oct 30, 1989Jun 9, 1992Stratasys, Inc.Apparatus and method for creating three-dimensional objectsUS5122441Oct 29, 1990Jun 16, 1992E. I. 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KeremesReal time cap flattening during heat treat* Cited by examinerClassifications U.S. Classification106/400, 106/31.6, 106/31.13, 106/31.9International ClassificationC04B14/00Cooperative ClassificationB29C67/0081European ClassificationB29C67/00R6Legal EventsDateCodeEventDescriptionFeb 16, 2012ASAssignmentEffective date: 20120206Owner name: 3D SYSTEMS, INC., SOUTH CAROLINAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:Z CORPORATION;REEL/FRAME:027716/0929Apr 23, 2008ASAssignmentOwner name: Z CORPORATION, MASSACHUSETTSFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WILLIAMS, DEREK X.;REEL/FRAME:020843/0043Effective date: 20080328RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google