WO2015003278A1 - Coating process for manufacturing a three-dimensional object, assembly for performing said process and object obtained by said process - Google Patents

Coating process for manufacturing a three-dimensional object, assembly for performing said process and object obtained by said process Download PDF

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Publication number
WO2015003278A1
WO2015003278A1 PCT/CH2013/000124 CH2013000124W WO2015003278A1 WO 2015003278 A1 WO2015003278 A1 WO 2015003278A1 CH 2013000124 W CH2013000124 W CH 2013000124W WO 2015003278 A1 WO2015003278 A1 WO 2015003278A1
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WO
WIPO (PCT)
Prior art keywords
soluble
coating
matter
plasma torch
bio
Prior art date
Application number
PCT/CH2013/000124
Other languages
French (fr)
Inventor
Georges ABOU JAOUDÉ
Christopher Wasserman
Original Assignee
Terolab Surface Medical Holding Sa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Terolab Surface Medical Holding Sa filed Critical Terolab Surface Medical Holding Sa
Priority to PCT/CH2013/000124 priority Critical patent/WO2015003278A1/en
Priority to PCT/CH2014/000096 priority patent/WO2015003280A1/en
Publication of WO2015003278A1 publication Critical patent/WO2015003278A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18—After-treatment
    • C23C4/185—Separation of the coating from the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying

Definitions

  • the present invention relates to a coating process for building an object, a container usable for the cell growth, or an implantable auto regulated diffusion capsule, or an implant or a part of an implant, comprising at least one three- dimensional pattern.
  • the present invention relates also to an assembly for performing said coating process for building an object.
  • the invention finally relates to an object, including a container usable for cell growth, or an implantable auto regulated diffusion capsule, or an implant or a part of an implant having shape and measurements which are adapted to its function adapted to one of that uses.
  • the containers for cells growth and similar kind of objects are mainly used in the biomedical and research area.
  • the main feature of that kind of typical objects is to be manufactured with biocompable material.
  • the same specific features are requested for implants and therefore special metals and/or metal alloys such as titanium and titanium alloys are widely used.
  • the need for implants made of biocompatible and bio soluble material is continually rising and the prior art solutions do not supply satisfactory answers to resolve the technical and biomedical problems. It is very important to know that the combination of rapid prototyping and cat scans or mri is at the heart of research and surgery. Disclosure of Invention
  • the process of the invention offers a new technology for building an object according to the above preamble, characterized in that the coating of the at least one three-dimensional pattern is at least partially made of at least one bio soluble material with at least one bio-compatible matter, by means of a plasma torch spouting at least one molten bio soluble matter and/or at least one biocompatible matter on said three-dimensional pattern.
  • the at least one bio-compatible matter is preferably a powder being at least sequentially inserted into said plasma torch.
  • the at least one bio soluble matter is a powder being at least sequentially inserted into said plasma torch.
  • a soluble three-dimensional object is advantageously coated to build at least a first coated layer in a first step of the process, and then object is removed in a second step of the process.
  • Further coating steps are performed to reinforce said first coated layer and to realize a three-dimensional pattern having defined shape and dimensions.
  • a rapid prototyping system may be used to build at least one soluble part
  • a plasma torch may be used to build up a non soluble part over the at least one soluble part and at least one non soluble part may be built over the non soluble part.
  • the present invention relates further to a coating device as defined above, characterized in that it comprises means for coating the at least one three- dimensional pattern at least partially with least one bio soluble material and with at least one bio-compatible matter, said means comprising a plasma torch designed for spouting at least one molten bio soluble matter and/or at least one biocompatible matter on said three-dimensional pattern.
  • the said plasma torch is preferably designed to spout at least sequentially at least one bio-compatible powder matter.
  • the said plasma torch is preferably designed to spout at least sequentially at least one bio soluble powder matter.
  • the device comprises advantageously means for coating a soluble three- dimensional object to build at least a first coated layer and means for removing the object after said coating step.
  • the coating device comprises preferably a rapid prototyping system for building at least one soluble part, in that the plasma torch is designed for building up a non soluble part over the at least one soluble part and in that the plasma torch is designed for building up at least one non soluble part over the non soluble part.
  • Figure 1 is a general view showing a first embodiment of a device for performing the process of the present invention
  • Figure 2 is a similar view as in figure 1 , showing a second embodiment of a device for performing the process of the present invention
  • Figure 3 is a similar view as in figure 1 showing said first embodiment of the device for performing the process of the present invention to build an object like a capsule,
  • Figure 4A represents the device of figure 1 for building a three-dimensional capsule d which can be pre-coated
  • Figure 4B represents an enlarged view of the precoated capsule of Figure 4A
  • Figure 5 represents the capsule of figure 4 in which a coated part is removed from a pre-coated part thereof
  • Figure 6 shows a similar coating device used to coat a soluble three- dimensional object
  • Figures 7A to 71 show further embodiment of a device for building three- dimensional objects comprising a rapid prototyping system and a multi coating device for realizing soluble parts and non-soluble parts.
  • One of the preferred applications of the present invention is to build three- dimensional objects for cell growth especially for creating implantable auto regulated diffusion capsules and manufacturing three-dimensional implants.
  • the main feature of the process of the invention is to combine biocompatible matter and bio soluble mater for realizing the three-dimensional objects.
  • the process can address different coating methods but the mode for carrying out the coating process of the invention will mainly be plasma model for HAP coating.
  • FIG. 1 showing a first device for performing the process of the invention consisting in coating petri boxes with variable HAP densities, thicknesses and combination of more or less accelerated matter to generate different environments.
  • the object of the coating is to realize petri boxes which enhance the cells or bacteria growth.
  • Each environment will be considered three-dimensional and according to the variation of the speed of particles, more or less soluble matter and variable density and porosity.
  • the petri boxes or any other container can be pre-coated with soluble or non-soluble structure.
  • A is the projecting vector
  • b and c or more are injection units for powder such as HAP that will crystallize differently according to the variable penetration angles.
  • the coating head A and the receptor d are displaced in XYZ directions depending on the wanted result in terms of density, speed and/or pattern generation.
  • the process of the invention consists in coating petri boxes in a similar manner as according to figure 1 , but adding a moving mask E between the projecting vector A and the receptor d.
  • the movable mask E can move in XYZ directions and regulate the generation of three-dimensional patterns on the used support such as the petri box.
  • the combination of both the method according to figure 1 and the method according to figure 2 will generate a more regulated space than using only the device of figurel .
  • the process of the invention consists in coating a three- dimensional object d which is water soluble, bio soluble or just simply removable by any chemical or mechanical means. The objects extracted from the coated soluble mold become containers for diffusible products.
  • the HAP three-dimensional capsule has a defined geometry, encloses products and will diffuse with regulation that is not electronically managed but with it's intrinsic geometry, density and porosity.
  • the coating device is similar as that of figure 1 .
  • the figure 4 shows a three-dimensional capsule d which can be pre-coated with a non adherent matter for a HAP or another coating product, in order to generate bio compatible and soluble capsules.
  • the coating device is similar as that of figure 1 .
  • the figure 5 shows the coated part di which is removed from the pre-coated part d 2 .
  • a similar coating device is used to coat a soluble three- dimensional object, and further to remove the object and maintain just the reinforced coating as an implant by itself and not a coating.
  • the coating system is coupled with a two component rapid prototyping system for building a soluble part and a non-soluble part.
  • the object is built layer by layer on a xyz displacement table and moved under the coating device when HAP deposit is required.
  • Figure 7A shows a rapid prototyping system head A using a first building device b to build a soluble part 100 on a movable plate D.
  • a separation wall E is provided to separate the rapid prototyping system head A from the plasma torch F.
  • Figure 7B shows the prototyping system head A using a second building device c to build up a non soluble part 1 10 over the soluble part 100.
  • Figure 7C shows the device in which the separation wall E is removed or moved up.
  • Figure 7D shows the device in which the movable plate is moved under the plasma torch F.
  • Figure 7E shows the device in which the separation wall E is moved down and the parts are coated by the plasma torch F.
  • Figure 7F shows the device in which the separation wall E is moved up.
  • Figure 7G shows the device in which the movable plate D is moved back under the building head A of the rapid prototyping system.
  • Figure 7H shows the device in which the separation wall E is moved down between the building system head A and the coating torch F.
  • Figure 71 shows the use of the building head A and especially the first building device b thereof to build non soluble part 120 over the non soluble part 1 10.

Abstract

The invention concerns a process and a device for coating process for building an object, and a container usable for the cell growth, or an implantable auto regulated diffusion capsule, or an implant or a part of an implant, comprising at least one three-dimensional pattern. The device comprises a rapid prototyping system head (A) using a first building device (b) to build a soluble part (100) on a movable plate (D). A separation wall (E) is provided to separate the rapid prototyping system head (A) from a plasma torch (F). The first building device (b) building head (A) is designed to build non soluble part (120) over a non soluble part (110) which is build over the soluble part (100).

Description

COATING PROCESS FOR MANUFACTURING A THREE-DIMENSIONAL OBJECT, ASSEMBLY FOR PERFORMING SAID PROCESS AND OBJECT OBTAINED BY SAID PROCESS Technical Field
The present invention relates to a coating process for building an object, a container usable for the cell growth, or an implantable auto regulated diffusion capsule, or an implant or a part of an implant, comprising at least one three- dimensional pattern.
The present invention relates also to an assembly for performing said coating process for building an object.
The invention finally relates to an object, including a container usable for cell growth, or an implantable auto regulated diffusion capsule, or an implant or a part of an implant having shape and measurements which are adapted to its function adapted to one of that uses.
Background Art
The containers for cells growth and similar kind of objects are mainly used in the biomedical and research area. The main feature of that kind of typical objects is to be manufactured with biocompable material. The same specific features are requested for implants and therefore special metals and/or metal alloys such as titanium and titanium alloys are widely used. The need for implants made of biocompatible and bio soluble material is continually rising and the prior art solutions do not supply satisfactory answers to resolve the technical and biomedical problems. It is very important to know that the combination of rapid prototyping and cat scans or mri is at the heart of research and surgery. Disclosure of Invention
The process of the invention offers a new technology for building an object according to the above preamble, characterized in that the coating of the at least one three-dimensional pattern is at least partially made of at least one bio soluble material with at least one bio-compatible matter, by means of a plasma torch spouting at least one molten bio soluble matter and/or at least one biocompatible matter on said three-dimensional pattern.
The at least one bio-compatible matter is preferably a powder being at least sequentially inserted into said plasma torch.
The at least one bio soluble matter is a powder being at least sequentially inserted into said plasma torch. A soluble three-dimensional object is advantageously coated to build at least a first coated layer in a first step of the process, and then object is removed in a second step of the process.
Further coating steps are performed to reinforce said first coated layer and to realize a three-dimensional pattern having defined shape and dimensions.
A rapid prototyping system may be used to build at least one soluble part, a plasma torch may be used to build up a non soluble part over the at least one soluble part and at least one non soluble part may be built over the non soluble part.
The present invention relates further to a coating device as defined above, characterized in that it comprises means for coating the at least one three- dimensional pattern at least partially with least one bio soluble material and with at least one bio-compatible matter, said means comprising a plasma torch designed for spouting at least one molten bio soluble matter and/or at least one biocompatible matter on said three-dimensional pattern. The said plasma torch is preferably designed to spout at least sequentially at least one bio-compatible powder matter. The said plasma torch is preferably designed to spout at least sequentially at least one bio soluble powder matter.
The device comprises advantageously means for coating a soluble three- dimensional object to build at least a first coated layer and means for removing the object after said coating step.
The coating device comprises preferably a rapid prototyping system for building at least one soluble part, in that the plasma torch is designed for building up a non soluble part over the at least one soluble part and in that the plasma torch is designed for building up at least one non soluble part over the non soluble part.
Brief Description of Drawings
The invention will now be described, by way of examples, with reference to the accompanying drawings, in which:
Figure 1 is a general view showing a first embodiment of a device for performing the process of the present invention, Figure 2 is a similar view as in figure 1 , showing a second embodiment of a device for performing the process of the present invention,
Figure 3 is a similar view as in figure 1 showing said first embodiment of the device for performing the process of the present invention to build an object like a capsule,
Figure 4A represents the device of figure 1 for building a three-dimensional capsule d which can be pre-coated, Figure 4B represents an enlarged view of the precoated capsule of Figure 4A,
Figure 5 represents the capsule of figure 4 in which a coated part is removed from a pre-coated part thereof,
Figure 6 shows a similar coating device used to coat a soluble three- dimensional object, and Figures 7A to 71 show further embodiment of a device for building three- dimensional objects comprising a rapid prototyping system and a multi coating device for realizing soluble parts and non-soluble parts.
Mode for Carrying Out the Invention
One of the preferred applications of the present invention is to build three- dimensional objects for cell growth especially for creating implantable auto regulated diffusion capsules and manufacturing three-dimensional implants. The main feature of the process of the invention is to combine biocompatible matter and bio soluble mater for realizing the three-dimensional objects. The process can address different coating methods but the mode for carrying out the coating process of the invention will mainly be plasma model for HAP coating.
The need for such a technology is mainly, but not only located in the field of biomedical experimental and research area. Three-dimensional objects or recipients made of biocompatible and bio soluble material have a wide range of applications mainly in stand-alone implants with only the coating material, implantable recipients for cells to enhance tissue growth or pre grown tissue on the recipient, cells diffusion from non-active containers regulated by porosity and bio soluble ingredients, and medical diffusion from non active containers regulated by porosity and bio soluble ingredients. According to figure 1 , showing a first device for performing the process of the invention consisting in coating petri boxes with variable HAP densities, thicknesses and combination of more or less accelerated matter to generate different environments. The object of the coating is to realize petri boxes which enhance the cells or bacteria growth. Each environment will be considered three-dimensional and according to the variation of the speed of particles, more or less soluble matter and variable density and porosity. In order to generate more complex three-dimensional coating the petri boxes or any other container can be pre-coated with soluble or non-soluble structure.
In figure 1 , A is the projecting vector, b and c or more, are injection units for powder such as HAP that will crystallize differently according to the variable penetration angles. The coating head A and the receptor d are displaced in XYZ directions depending on the wanted result in terms of density, speed and/or pattern generation.
According to figure 2, the process of the invention consists in coating petri boxes in a similar manner as according to figure 1 , but adding a moving mask E between the projecting vector A and the receptor d. The movable mask E can move in XYZ directions and regulate the generation of three-dimensional patterns on the used support such as the petri box. The combination of both the method according to figure 1 and the method according to figure 2 will generate a more regulated space than using only the device of figurel . According to figure 3, the process of the invention consists in coating a three- dimensional object d which is water soluble, bio soluble or just simply removable by any chemical or mechanical means. The objects extracted from the coated soluble mold become containers for diffusible products. The HAP three-dimensional capsule has a defined geometry, encloses products and will diffuse with regulation that is not electronically managed but with it's intrinsic geometry, density and porosity. The coating device is similar as that of figure 1 , The figure 4 shows a three-dimensional capsule d which can be pre-coated with a non adherent matter for a HAP or another coating product, in order to generate bio compatible and soluble capsules. The coating device is similar as that of figure 1 .
The figure 5 shows the coated part di which is removed from the pre-coated part d2.
According to the figure 6 a similar coating device is used to coat a soluble three- dimensional object, and further to remove the object and maintain just the reinforced coating as an implant by itself and not a coating. The coating system is coupled with a two component rapid prototyping system for building a soluble part and a non-soluble part. The object is built layer by layer on a xyz displacement table and moved under the coating device when HAP deposit is required.
The process for building this kind of objects will be described in detail hereunder and the successive steps are illustrated by the device of figures 7A to 71. Figure 7A shows a rapid prototyping system head A using a first building device b to build a soluble part 100 on a movable plate D. A separation wall E is provided to separate the rapid prototyping system head A from the plasma torch F. Figure 7B shows the prototyping system head A using a second building device c to build up a non soluble part 1 10 over the soluble part 100. Figure 7C shows the device in which the separation wall E is removed or moved up. Figure 7D shows the device in which the movable plate is moved under the plasma torch F. Figure 7E shows the device in which the separation wall E is moved down and the parts are coated by the plasma torch F. Figure 7F shows the device in which the separation wall E is moved up. Figure 7G shows the device in which the movable plate D is moved back under the building head A of the rapid prototyping system. Figure 7H shows the device in which the separation wall E is moved down between the building system head A and the coating torch F. Figure 71 shows the use of the building head A and especially the first building device b thereof to build non soluble part 120 over the non soluble part 1 10.
Similar steps can be restarted to build progressively and coat successive layers when needed.

Claims

1 . A coating process for building an object, especially a container usable for the cell growth, or an implantable auto regulated diffusion capsule, or an implant or a part of an implant, comprising at least one three-dimensional pattern, characterized in that the coating of the at least one three-dimensional pattern is at least partially made of at least one bio soluble material with at least one biocompatible matter, by means of a plasma torch spouting at least one molten bio soluble matter and/or at least one biocompatible matter on said three- dimensional pattern.
2. A coating process according to claim 1 , characterized in that at least one bio-compatible matter is a powder being at least sequentially inserted into said plasma torch.
3. A coating process according to claim 1 , characterized in that at least one bio soluble matter is a powder being at least sequentially inserted into said plasma torch.
4, A coating process according to claim 1 , characterized in that a soluble three-dimensional object is coated to build at least a first coated layer in a first step of the process, in that the object is removed in a second step of the process.
5. A coating process according to claim 4, characterized in that further coating steps are performed to reinforce said first coated layer and to realize a three-dimensional pattern having predetermined shape and dimensions.
6. A coating process according to claim 1 , characterized in that a rapid prototyping system is used to build at least one soluble part, in that a plasma torch is used to build up a non soluble part over the at least one soluble part and in that at least one non soluble part is built over the non soluble part.
7, A coating device for building an object, especially a container usable for the cell growth, or an implantable auto regulated diffusion capsule, or an implant or a part of an implant, comprising at least one three-dimensional pattern, characterized in that it comprises means for coating the at least one three- dimensional pattern at least partially with least one bio soluble material and with at least one bio-compatible matter, said means comprising a plasma torch designed for spouting at least one molten bio soluble matter and/or at least one biocompatible matter on said three-dimensional pattern.
8. The coating device according to claim 7 characterized in that the said plasma torch is designed to spout at least sequentially at least one biocompatible powder matter.
9. The coating device according to claim 7 characterized in that the said plasma torch is designed to spout at least sequentially at least one bio soluble powder matter.
10. The coating device according to claim 7 characterized in that it comprises means for coating a soluble three-dimensional object to build at least a first coated layer and means for removing the object after said coating step.
1 1 . The coating device according to claim 7 characterized in that it comprises a rapid prototyping system for building at least one soluble part, in that the plasma torch is designed for building up a non soluble part over the at least one soluble part and in that the plasma torch is designed for building up at least one non soluble part over the non soluble part.
PCT/CH2013/000124 2013-07-11 2013-07-11 Coating process for manufacturing a three-dimensional object, assembly for performing said process and object obtained by said process WO2015003278A1 (en)

Priority Applications (2)

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PCT/CH2013/000124 WO2015003278A1 (en) 2013-07-11 2013-07-11 Coating process for manufacturing a three-dimensional object, assembly for performing said process and object obtained by said process
PCT/CH2014/000096 WO2015003280A1 (en) 2013-07-11 2014-07-07 Process for building a three-dimensional object, device for building said object

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PCT/CH2013/000124 WO2015003278A1 (en) 2013-07-11 2013-07-11 Coating process for manufacturing a three-dimensional object, assembly for performing said process and object obtained by said process

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PCT/CH2014/000096 WO2015003280A1 (en) 2013-07-11 2014-07-07 Process for building a three-dimensional object, device for building said object

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CN107287546B (en) * 2016-04-05 2019-10-25 武汉理工大学 A kind of heat insulation cup and preparation method thereof using the preparation of thermal spraying 3D printing technique

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WO1997041273A1 (en) * 1996-04-30 1997-11-06 Flametal S.P.A. Process for the preparation of hydroxyapatite coatings
JP2006131469A (en) * 2004-11-08 2006-05-25 National Institute Of Advanced Industrial & Technology Apatite composite material coated with apatite having crystal orientation
US20080241350A1 (en) * 2007-03-26 2008-10-02 Howmedica Osteonics Corp. Method for fabricating a medical component from a material having a high carbide phase
US20110300188A1 (en) * 2010-06-02 2011-12-08 Shimp Lawrence A Glassy calcium phosphate particulates, coatings and related bone graft materials

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CN102242329A (en) * 2011-06-07 2011-11-16 昆山市瑞捷精密模具有限公司 Iron-based die with function of self-lubricating manufactured by adopting electric arc spraying

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
WO1997041273A1 (en) * 1996-04-30 1997-11-06 Flametal S.P.A. Process for the preparation of hydroxyapatite coatings
JP2006131469A (en) * 2004-11-08 2006-05-25 National Institute Of Advanced Industrial & Technology Apatite composite material coated with apatite having crystal orientation
US20080241350A1 (en) * 2007-03-26 2008-10-02 Howmedica Osteonics Corp. Method for fabricating a medical component from a material having a high carbide phase
US20110300188A1 (en) * 2010-06-02 2011-12-08 Shimp Lawrence A Glassy calcium phosphate particulates, coatings and related bone graft materials

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