GB2414231A - Porous silicon - Google Patents
Porous silicon Download PDFInfo
- Publication number
- GB2414231A GB2414231A GB0411358A GB0411358A GB2414231A GB 2414231 A GB2414231 A GB 2414231A GB 0411358 A GB0411358 A GB 0411358A GB 0411358 A GB0411358 A GB 0411358A GB 2414231 A GB2414231 A GB 2414231A
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- GB
- United Kingdom
- Prior art keywords
- silicon
- unitary body
- particles
- bonded
- porous
- Prior art date
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 149
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 138
- 239000010703 silicon Substances 0.000 claims abstract description 138
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000002210 silicon-based material Substances 0.000 claims abstract description 5
- 239000011856 silicon-based particle Substances 0.000 claims description 83
- 239000002245 particle Substances 0.000 claims description 14
- 238000007743 anodising Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 abstract description 11
- 238000007596 consolidation process Methods 0.000 abstract description 4
- 210000000988 bone and bone Anatomy 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 description 15
- 238000002048 anodisation reaction Methods 0.000 description 10
- 206010028980 Neoplasm Diseases 0.000 description 7
- 229910052785 arsenic Inorganic materials 0.000 description 6
- 201000011510 cancer Diseases 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- -1 B. Ge Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910008045 Si-Si Inorganic materials 0.000 description 3
- 229910006411 Si—Si Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
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- 235000012431 wafers Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 208000003174 Brain Neoplasms Diseases 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- GHASVSINZRGABV-UHFFFAOYSA-N Fluorouracil Chemical compound FC1=CNC(=O)NC1=O GHASVSINZRGABV-UHFFFAOYSA-N 0.000 description 1
- 101000904173 Homo sapiens Progonadoliberin-1 Proteins 0.000 description 1
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- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 208000024313 Testicular Neoplasms Diseases 0.000 description 1
- 206010057644 Testis cancer Diseases 0.000 description 1
- JXLYSJRDGCGARV-WWYNWVTFSA-N Vinblastine Natural products O=C(O[C@H]1[C@](O)(C(=O)OC)[C@@H]2N(C)c3c(cc(c(OC)c3)[C@]3(C(=O)OC)c4[nH]c5c(c4CCN4C[C@](O)(CC)C[C@H](C3)C4)cccc5)[C@@]32[C@H]2[C@@]1(CC)C=CCN2CC3)C JXLYSJRDGCGARV-WWYNWVTFSA-N 0.000 description 1
- 229940122803 Vinca alkaloid Drugs 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 230000000340 anti-metabolite Effects 0.000 description 1
- 229940100197 antimetabolite Drugs 0.000 description 1
- 239000002256 antimetabolite Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229960004630 chlorambucil Drugs 0.000 description 1
- JCKYGMPEJWAADB-UHFFFAOYSA-N chlorambucil Chemical compound OC(=O)CCCC1=CC=C(N(CCCl)CCCl)C=C1 JCKYGMPEJWAADB-UHFFFAOYSA-N 0.000 description 1
- DQLATGHUWYMOKM-UHFFFAOYSA-L cisplatin Chemical compound N[Pt](N)(Cl)Cl DQLATGHUWYMOKM-UHFFFAOYSA-L 0.000 description 1
- 229960004316 cisplatin Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
- 229940127089 cytotoxic agent Drugs 0.000 description 1
- 239000002254 cytotoxic agent Substances 0.000 description 1
- 231100000599 cytotoxic agent Toxicity 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 229960004679 doxorubicin Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
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- 229960002949 fluorouracil Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 208000015486 malignant pancreatic neoplasm Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 201000002528 pancreatic cancer Diseases 0.000 description 1
- 208000008443 pancreatic carcinoma Diseases 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 201000003120 testicular cancer Diseases 0.000 description 1
- 230000008467 tissue growth Effects 0.000 description 1
- 229960003048 vinblastine Drugs 0.000 description 1
- JXLYSJRDGCGARV-XQKSVPLYSA-N vincaleukoblastine Chemical compound C([C@@H](C[C@]1(C(=O)OC)C=2C(=CC3=C([C@]45[C@H]([C@@]([C@H](OC(C)=O)[C@]6(CC)C=CCN([C@H]56)CC4)(O)C(=O)OC)N3C)C=2)OC)C[C@@](C2)(O)CC)N2CCC2=C1NC1=CC=CC=C21 JXLYSJRDGCGARV-XQKSVPLYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
- H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A method for fabricating a macroporous silicon material comprises consolidation of particulate silicon. The particulate silicon may treated with hydrofluoric acid prior to the consolidation step. A uniaxial pressure of between 1,000 and 5,000 psi (6895-34470 kPa) is then applied by means of a cold pressing device (1). The consolidated product may be anodised to form further, smaller micropores within the material. The material may be used in the body for repairing of replacing bone. The consolidated silicon material may be crushed to form a partially surface porous silicon.
Description
241 423 1 New silicon structure and method of fabrication therefor The
present invention relates to a new silicon structure and a new process for fabricating a silicon structure. More specifically the present invention concerns a new process of fabricating macroporous silicon, and a new macroporous silicon product. The process involves the consolidation of a silicon particulate product, followed by anodisation of the consolidated product. The resulting macroporous silicon product comprises macropores that are substantially surrounded by microporous and/or mesoporous silicon.
Porous silicon has properties that allow it to be used for a variety of medical uses. For example it is a biocompatible and resorbable material as described in WO 9706101; it can be used as a scaffold for the repair or replacement of damaged bone as described in WO 0195952; it can be used in dermatological compositions as described in WO 0215863; and it can be used in a variety of diagnostic devices as described in WO 03015636. The IS biological properties of porous silicon are often dependent upon porosity and pore size.
Porous silicon has been formed that has a porosity as low as 2%, and in excess of 90%; it may be categorized by its pore size: microporous silicon contains pores having a diameter less than 20 A, mesoporous silicon contains pores having a diameter in the range 20 A to 500 A; and macroporous silicon contains pores having a diameter greater than 500 A. The two main methods by which porous silicon can be fabricated are: (a) by anodization, and (b) by stain etching. Anodisation Epically involves the immersion of a solid sample of silicon, such as a bulk crystalline silicon wafer, in hydrofluoric acid solution. An electrical contact is made with the sample of silicon, a potential difference being applied between the 2s silicon and a second electrode also placed in the solution. The HF etches the.silicon to create pores and hence porous silicon is formed. Preferably the sample is semiconducting throughout its volume, to allow a uniform potential difference to be established.
Stain etching involves the immersion of a silicon sample in a hydrofluoric acid solution containing a strong oxidising agent. No electrical contact is made with the silicon, and no potential is applied. The hydrofluoric acid etches the surface of the silicon to create pores.
The technique is commonly used to etch relatively small particles of silicon, since it would be difficult to attach an electrode to each small particle.
One of the main disadvantages of anodisation is its relatively low throughput and hence high cost. The use of an electrochemical cell reduces the speed at which silicon can be processed, hence increasing expense. Further, the silicon used for anodisation is preferably semiconducting throughout its volume, and this typically means that relatively expensive silicon wafers are employed.
Stain etching allows the use of particulate silicon that may be obtained at a lower price than silicon wafers, and does not involve the use of a time consuming electrochemical process.
However, it is easier to control the pore size and/or porosity of porous silicon fabricated by anodisation than by stain etch techniques.
The following documents provide background information that is relevant to the present application. US 5,164,138 describes a process for manufacturing an article having particles comprising a silicon based material; the particles are bonded to one another by reaction with a liquid agent. US 4,357,443 describes a process for producing a silicon containing article comprising the step of coating the particle with boron oxide. US 4,040,848 describes a process for producing a polycrystalline silicon sintered body which comprises the step of forming a particulate mixture of silicon powder and boron. US 4,865,245 describes a method of joining together two semiconductor devices, each having a number of metallic contacts. US 6,126,894 describes a method for producing a high density sintered article from iron-silicon alloys. US 4,818,482 describes a process for producing workplaces comprising water atomising a metal alloy. US 5,711,866 describes a process for consolidating powders comprising the step of removing an oxide from the surface of a metal coated composite. US 6,057,469 describes a process for the preparation of a silicon powder comprising the step of grinding metallurgical grade silicon.
It is an objective of the present invention to at least partly solve at least some of the above mentioned problems. It is a further objective of the present invention to provide a process that allows the low cost, rapid fabrication of porous silicon having a well defined porosity and pore size.
According to one aspect the invention provides a process for fabricating a silicon material, the process comprising the steps: (a) taking a silicon particulate product comprising a multiplicity of free silicon particles; and (b) consolidating at least part of the silicon particulate product to form a multiplicity of bonded silicon particles, each of the bonded silicon particles being bonded to at least one of the other bonded silicon particles.
At least one of the bonds formed between at least two of the bonded silicon particles may be a covalent Si-Si bond. At least some of the bonded silicon particles may be Si-Si covalently bonded.
Steps (a) and (b) may be performed in such a manner that a silicon unitary body is formed, the silicon unitary body comprising at least some of the bonded silicon particles.
Steps (a) and (b) may be performed in such a manner that the silicon unitary body comprises at least 10 bonded silicon particles. Steps (a) and (b) may be performed in such a manner that the silicon unitary body comprises at least 100 bonded silicon particles.
Steps (a) and (b) may be performed in such a manner that the silicon unitary body comprises at least 1,000 bonded silicon particles. Steps (a) and (b) may be performed in such a manner that the silicon unitary body comprises between 10 and 1 o,6 bonded silicon particles. Steps (a) and (b) may be performed in such a manner that the silicon unitary body comprises between 104 and 10'6 bonded silicon particles.
Steps (a) and (b) may be performed in such a manner that the silicon unitary body has a surface area greater than or equal to 100 cm2 per gram of silicon.
The unitary body may be porous, the pores being formed by interstices between the bonded silicon particles. This porosity may result in a relatively high surface area.
Steps (a) and (b) may be performed in such a manner that a silicon unitary body is formed having a Fracture strength between 70 MPa and 7, 000 MPa.
Steps (a) and (b) may be performed in such a manner that a silicon unitary body is formed having an electrical resistivity between 10 K Qcm and 10 SQcm.
The formation of silicon - silicon covalent bonds between the bonded silicon particles may result in the unitary body having a relatively high mechanical strength and low electrical resistivity.
Steps (a) and (b) may be performed in such a manner that each of the bonded silicon particles from which the unitary is formed, are integral with each of the other bonded silicon particles from which the silicon unitary body is formed.
The process may comprise the further step (r) of chemically reducing part of the silicon particulate product. The step (r) may be performed prior to step (b). The step (r) may comprise the step of substantially removing any silicon oxide from at least part of the surface of the free silicon particles. The step (r) may comprise the step of treating at least some of the free silicon particles with a reducing agent. The step (r) may comprise the step of treating at least some of the free silicon particles with a reducing agent selected from one or more of: NaOH, KOH, and HF. The step (r) may comprise the step of treating at least some of the free silicon particles with a solution of hydrofluoric acid. The step (r) may comprise the step of treating at least some of the free silicon particles with HE vapour. The step (r) may be performed in such a manner that Si-H bonds are formed at the surface of at least some of the free silicon particles.
The treatment of the free silicon particles with hydrofluoric acid is advantageous because it results in the formation of free silicon particles having a surface that is at least partly hydrogen terminated, and because it at least partly removes any oxygen atoms that were bonded to the surface of the free silicon particles.
It has been discovered that the presence of oxygen atoms at the surface of the free silicon particles makes it more difficult to consolidate the silicon particulate product. In other words the presence of oxygen bonded to the surface of the silicon makes it more difficult to form Si-Si covalent bonds between the bonded silicon particles.
The presence of the hydrogen atoms at the surface of the free silicon particles is also advantageous, because this helps to prevent oxygen rebonding to the silicon surface prior to consolidation.
Step (b) may comprise the step (p) of applying pressure to at least some of the free silicon particles.
Step (b) may comprise the steps: (ci) of placing at least some of the free silicon particles in s a container; and (all) reducing the volume of the container.
Step (ci) and step (all) may be performed in such a manner that pressure is applied to at least some of the free silicon particles contained in the container.
Step (b) may comprise the steps: (cii) placing at least some of the free silicon particles in a volume enclosed by at least part of a mould; and (did) reducing the enclosed volume.
Step (cii) and step (did) may be performed in such a manner that pressure is applied to at least some of the free silicon particles contained in the mould.
The silicon particulate product may comprise semiconducting silicon. The particulate silicon product may comprise one or more of: polycrystalline silicon, amorphous silicon, bulk crystalline silicon, and metallurgical grade silicon.
At least some of the free silicon particles may comprise semiconducting silicon. At least some of the free silicon particles may comprise one or more of: polycrystalline silicon, amorphous silicon, bulk crystalline silicon, and metallurgical grade silicon.
The silicon particulate product may comprise porous silicon. At least some of the free silicon particles may comprise porous silicon. Each of the free silicon particles may comprise porous silicon.
The silicon particulate product may comprise one or more of the following elements: Y. P. Sb, In, Fe, As, La, Ca, Pd. Sr, 1, Co, Ir, B. Ge, Cu. Pb, Sn, and Au. At least some of the free silicon particles may comprise one or more of the following elements: Y. P. Sb, In, Fe, As,La,Ca,Pd,Sr,l,Co, lr,B,Ge,Cu,Pb,Sn,and Au.
Preferably the silicon particulate product may comprise one or more of the following elements: Y. B. P. and Sn. Preferably at least some of the free silicon particles may comprise one or more of the following elements: Y. B. P. and Sn.
The process may comprise the further step (e) of porosifying at least part of the silicon unitary body. The process may comprise the further step (e) of porosifying at least part of the silicon unitary body by anodising the silicon unitary body in a solution of hydrofluoric acid. The process may comprise the further step (e) of porosifying at least part of the silicon unitary body by anodising the silicon unitary body in a solution of hydrofluoric acid, the solution comprising a surfactant. The surfactant may comprise one or more of: ethanol, methanol, and acetic acid.
lo The use of a surfactant may assist the ingress of the hydrofluoric acid solution into pores located between the bonded silicon particles.
The process may comprise the further step (e) of porosifying at least part of the silicon unitary body by stain etching the silicon unitary body in a solution of hydrofluoric acid.
The step (e) may be preceded by the step of attaching at least one electrode to the silicon unitary body.
The unitary body may comprise a plurality of macropores, each pore being formed at least partly by the interstices between the bonded silicon particles. The mean size of the macropores contained in the unitary body may have a size between 500 and 200 microns.
The step (e) may comprise the step of allowing a solution of hydrofluoric acid to pass into at least one of the macropores of the unitary body. The step (e) may comprise the step of allowing a solution of hydrofluoric acid to pass into substantially all the macropores of the unitary body.
The step (e) may be performed in such a manner that at least one of the bonded silicon particles is porosified throughout its volume. The step (e) may be performed in such a manner that at least one of the bonded silicon particles is porosified through substantially its whole volume. The step (e) may be performed in such a manner that substantially each of the bonded silicon particles is porosified through substantially its whole volume.
The fabrication of a macroporous silicon unitary body in this way, allows the anodization of a relatively inexpensive silicon particulate product. The particulate product is consolidated to form a unitary body that has sufficient mechanical strength and size to allow the attachment of an electrode, and hence anodization. The macroporous silicon body has a high surface area so that the yield of porous silicon is high relative to the amount of silicon used.
The step (e) may be performed in such a manner that microporous silicon and/or mesoporous silicon is formed in the silicon unitary body.
The process may comprise the further step (g), performed after step (e), of fragmenting the silicon unitary body. The step (g) may comprise the step of mechanically crushing the unitary body. The step (g) may comprise the step of ultrasonically fragmenting the unitary body. The step (g) may be performed in such a manner that a multiplicity of partially surface porous silicon particles are generated, the surface of each partially surface porous particle comprising a porous area and a non-porous area.
Each bonded silicon particle is bonded to at least one other bonded silicon particles, the bond or bonds being formed by applying pressure to two or more free silicon particles.
The silicon unitary body may comprise a first silicon bonded particle and a second silicon bonded particle. The first and second bonded silicon particles may be integral with each other without being in contact with each other.
Step (b) may comprise the step (h) of heating the silicon particulate product. Step (b) may comprise the step of heating the silicon particulate product to a temperature between 50 C and 500 C. The step (b) may comprise the step of maintaining the silicon particulate product at a substantially constant temperature.
The step (b) may comprise the step of maintaining the silicon particulate product at a temperature between -5 C and + 5 C for an interval of time. The step (b) may comprise the step of maintaining the silicon particulate product at a temperature between -20 C and + 20 C for an interval of time. The step (b) may comprise the step of maintaining the silicon particulate product at a temperature between -50 C and + 50 C for an interval of time.
The step (p) of applying a pressure to at least some of the free silicon particles may precede the step (h) of heating the silicon particulate product.
The step (b) may comprise the step of cold pressing at least part of the silicon particulate product.
The process may further comprise the step (i) of introducing a gas to a region in which at least some of the free silicon particles are located; the gas may comprise one or more of: nitrogen, helium, argon, and hydrogen.
The process may comprise the step (v) of removing a gas from a region in which at least some of the free silicon particles are located. The process may comprise the step of removing a gas from a region in which at least some of the free silicon particles are located in such a manner that the pressure is reduced to less than 1 mm Hg.
The step (b) and/or the step (h) may be performed after and/or during the step (i) and/or (v).
According to a further aspect, the invention provides a silicon unitary body comprising a silicon skeleton.
The silicon unitary body may further comprise (a) macroporous silicon having a mean pore size between 500 A and 200 microns; and (b) microporous silicon and/or mesoporous silicon.
The silicon unitary body may further comprise (a) macroporous silicon having a mean pore size between 500 A and 10 microns; and (b) microporous silicon and/or mesoporous silicon.
The silicon unitary body may further comprise (a) macroporous silicon having a mean pore size between 1 micron and 100 microns; and (b) microporous silicon and/or mesoporous silicon.
For the purposes of this specification an interconnected macropore is a macropore that is connected to at least one other macropore by one or more mesopores and/or one or more micropores.
The unitary body may comprise at least one interconnected macropore, the unitary body may comprise at least ten interconnected macropores. The unitary body may comprise at least 100 interconnected macropores. The unitary body may comprise at least 1,000 interconnected macropores.
lo The unitary body may comprise at least one interconnected macropore per 10 adjacent macropores. The unitary body may comprise at least one interconnected macropore per adjacent macropores. The unitary body may comprise at least one interconnected macropore per 1,000 adjacent macropores.
At least one of the macropores may be defined by at least part of a microporous surface and/or mesoporous silicon surface. At least some of the macropores may be defined by at least part of the microporous silicon surface and/or mesoprorous silicon surface. Each of the macropores may be defined by at least part of the microporous silicon surface and/or mesoprorous silicon surface.
At least some of the macropores may be formed in at least part of the silicon skeleton, and the or part of the silicon skeleton from which the macropores are formed may comprise at least part of the microporous silicon and/or mesoporous silicon.
The silicon unitary body may have an electrical resistivity between 10 K Qcm and 1 05Qcm The silicon unitary body may have a fracture strength between 70 MPa and 7,000 MPa.
The silicon unitary body may comprise one or more of the following elements: Y. P. Sb, In, Fe, As, La, Ca, Pd. Sr, 1, Co, Ir, B. Ge, Cu. Pb, Sn, and Au. The silicon unitary body may comprise one or more of the following isotopes: 90y, 32p, '24Sb, Gin, 59Fe, 76As, '40 La, 47 03Pd 89S 1311 Al soCO '92lr '2B oB'7'Ge,64cu,2o3pb and Au The silicon unitary body may form at least part of a cancer treatment device comprising a radionucleotide and/or a cyotoxic agent for use in the treatment of cancer.
The silicon unitary body may comprise a cancer treatment device comprising a radionucleotide selected from one or more of the following radionucleotides 90y, 32p, '24Sb, In, Fe, As, La, 47Ca, 103Pd, 39Sr, '3'1 2sl 60co 92lr '2B 'SIB 7'G 64C 203 s '93Au for use in the treatment of cancer.
The silicon unitary body may form at least part of a cancer treatment drug delivery device comprising a cytotoxic agent selected from one or more of: an alkylating agent such as chlorambucil, a cytotoxic antibody such as doxorubicin, an antimetabolite such as 0 fluorouracil, a vinca alkaloid such as vinblastine, a hormonal regulator such as GNRH, and a platinum compound such as cis platin.
The silicon unitary body may comprise a cancer treatment device having one or more of the following radionucleotides9oy,32p',24sb,41n ssFe 76As '40 La 47C '03Pd 89 131 '251 soCo, '921r, '2B, 7'Ge, 64Cu, 203Pb and '98Au for use in the treatment of one or more of the following cancers: prostate cancer, liver cancer, pancreatic cancer, breast cancer, lung cancer, brain cancer, and testicular cancer.
The unitary body may comprise an orthopaedic scaffold for use in the repair or replacement of bone.
The silicon unitary body may comprise semiconducting silicon. At least some of the free silicon particles may comprise one or more of: polycrystalline silicon, amorphous silicon, bulk crystalline silicon, and metallurgical grade silicon.
The silicon skeleton may comprise a multiplicity of bonded silicon particles, each bonded silicon particle being bonded to at least one of the other bonded silicon particles.
At least some of the bonded silicon particles may comprise one or more of macroporous silicon, mesoporous silicon, and microporous silicon.
According to a further aspect the invention provides a partially surface porous silicon particulate product comprising a multiplicity of partially surface porous silicon particles, the surface of each partially surface porous particle comprising a porous area and a non porous area.
At least one of the partially surface porous silicon particles may have at least two discrete non-porous areas. At least some of the partially porous silicon particles may each have two or more discrete non-porous areas.
At least one of the partially surface porous silicon particles may comprise a first non porous area and a second non-porous area, the first and second non-porous area being spatially separate from each other by a porous area.
to The partially surface porous silicon particulate product may comprise at least 100 partially surface porous silicon particles. The partially surface porous silicon particulate product may comprise between 100 and 10'5 partially surface porous silicon particles. The partially surface porous silicon particulate product may comprise between 100 and 105 partially surface porous silicon particles. The partially surface porous silicon particulate product may comprise between 100 and 103 partially surface porous silicon particles.
Substantially each partially surface porous silicon particle may have a size between 0.5 microns and 200 microns.
Between 10% and 90% of all of the partially surface porous silicon particles may have a size between 1 and 100 microns.
At least one of the partially surface porous silicon particles may comprise one or more of the following elements: Y. P. Sb, In, Fe, As, La, Ca, Pd. Sr, 1, Co, Ir, B. Ge, Cu. Pb, Sn, and Au. At least one of the partially surface porous silicon particles may comprise one or more of the followingisotopes9oy,32p''24sb,,41n s9Fe 76As '40 La 47C,03Pd as 13' Al 60co 92lr '2B ' B 7'Ge 64Cu, 203Pband'98Au The partially surface porous silicon particulate product may comprise one or more of the following elements: Y. P. Sb, In, Fe, As, La, Ca, Pd. Sr, 1, Co, Ir, B. Ge, Cu. Pb, Sn, and Au. The partially surface porous silicon particulate product may comprise one or more of i i t es 90Y 32p,24sb ''41n 59pe, 76As, '40La, 47ca, Pd. Sr, 1, 1, soCO '92lr '2B ' B 7,Ge 64Cu, 203Pb and '98Au.
The invention will now be described, by way of example only, with reference to the following drawings: Figure 1a shows a photograph of a cold pressing device used to fabricate a silicon unitary s body according to the present invention; Figure 1b shows a photograph of some of the components from which the figure 1a cold pressing device is formed; Figure 2a shows a SEM micrograph of part of a silicon unitary body according to the invention; and Figure 2b shows a SEM micrograph, of part of the same silicon unitary body shown in figure 2a, at a higher magnification.
A silicon particulate product having a mean particle size between 1 and 50 microns is treated with 40 wt % aqueous hydrofluoric acid to remove any oxide present at the particulate surface of the silicon product, and to create a hydrogen terminated particulate surface. The particulate product may comprise metallurgical grade silicon particles, that has been heavily p+ or n+ doped.
The hydrofluoric acid is removed from the silicon product by washing with deionised water before rapid drying on filter paper in air for 15 minutes. The particles are then rapidly loaded into a stainless steel cold pressing device 1, which is shown in Figure 1a. The drying and loading steps are carried out as quickly as possible to minimise or prevent reaction with oxygen, and to retain the hydrogen terminated particulate surface.
A uniaxial pressure of between 1,000 and 5,000 psi is then applied by means of the cold pressing device 1, the temperature of the silicon particulate product being maintained at 20 C. The resulting silicon unitary body is in the form of a cylindrical consolidated macroporous silicon block having a diameter of 5 mm and a length of 46 mm. A small opening is formed in cold pressing device to allow gas produced during the pressing process to escape.
Figure 1 b shows components, generally indicated by 2, of the stainless cold pressing device.
Figure 2a shows a SEM micrograph of part of a silicon unitary body 3 according to the s invention. The silicon body is in the form of a cylindrical block. The figure 2a image shows a fracture surface 4 at which the cylinder has been broken to more clearly show the macroporous nature of the unitary body. Figure 2b shows a higher magnification SEM micrograph, of the macroporous fracture surface 4.
An electrode is attached to the silicon block, it is then immersed in 1040 wt % aqueous hydrofluoric acid with a surfactant such as ethanol, and a current density of between 1 mAcm2 and 10 Acme, measured with respect to the external surface area of the block, is passed for between 1 to 200 minutes.
The hydrofluoric acid is able to pass into the macroporous network of the silicon block and the effect of anodisation is to form a porous layer on the interior surfaces of the macropores, and on the external surface of the silicon block.
Once anodisation is complete, the block is washed, by repeated immersion in deionised water, and then air dried.
Finally if a particulate product is required, the block may be mechanically crushed to yield a multiplicity of partially surface porous silicon particles. Each partially surface porous particle having a nonporous surface area, corresponding to the region that bonded it to an as adjacent silicon particle when still located in the block.
A unitary silicon body according to the invention may be used as a scaffold to provide protection for, or to assist, the regrowth of damaged or diseased tissue. A unitary body having an appropriate size and shape is placed in the region in which tissue regrowth is to occur. Macropores, having a size between 10, 000 Amy and 62, 500 gm2, formed in the unitary body allow the tissue to pass through the silicon scaffold. The scaffold may also comprise mesporous silicon, which may be engineered to erode once tissue growth is complete. This process is described in WO 0195952, which is herein incorporated by reference. 3s
Claims (13)
- Claims 1. A process for fabricating a silicon material, the processcomprising the steps: (a) taking a multiplicity of free silicon particles; and (b) consolidating at least some of the free silicon particles to form a silicon unitary body, the silicon unitary body comprising a multiplicity of bonded silicon particles, each bonded silicon particle being bonded to at least one of the other bonded silicon particles.lo
- 2. A process according to claim 1 characterized in that steps (a) and (b) are performed in such a manner that macropores are formed in silicon unitary body by interstices between the bonded silicon particles.
- 3. A process according to claim 2 characterized in that the process may comprise a further step of immersing the silicon unitary body in a solution of hydrofluoric acid and allowing the hydrofluoric acid solution to pass into at least some of the macropores.
- 4. A process according to claim 3 characterized in that the process further comprises the step of anodising the unitary body that has been immersed in the hydrofluoric acid solution.
- 5. A process according to claim 1 characterized in that steps (a) and (b) are performed in such a manner that two or more silicon unitary bodies are formed.
- 6. A process according to claim 1 characterized in that the process further comprises the step of treating at least some of the free silicon particles with hydrofluoric acid prior to step (b).
- 7. A product produced by a process according to any one of claims 1 to 6.
- 8. A partially surface porous silicon particulate product comprising a multiplicity of partially surface porous silicon particles, the surface of each partially surface porous particle comprising a porous area and a non-porous area.
- 9. A particulate product according to claim 8 characterized in that the particulate product 3s comprises at least 100 partially surface porous silicon particles.
- 10. A particulate product according to claim 8 characterized in that the mean particle size of the particulate product is between 0.5 microns and 200 microns.s
- 11. A particulate product according to claim 8 characterized in that at least one of the partially surface porous silicon particles has at least two discrete non-porous areas.
- 12. Macroporous silicon, characterized the macroporous silicon comprises at least one macropore that is connected to at least one other macropore by a micropore and/or a lo mesopore.
- 13. Macroporous silicon according to claim 12, characterized in that the silicon skeleton in which the macropores are formed substantially consists of microporous and/or mesoporous silicon.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0411358A GB2414231A (en) | 2004-05-21 | 2004-05-21 | Porous silicon |
| PCT/GB2005/001910 WO2005113467A1 (en) | 2004-05-21 | 2005-05-18 | Silicon structure |
| JP2007517409A JP2007537965A (en) | 2004-05-21 | 2005-05-18 | Silicon structure |
| CA002564591A CA2564591A1 (en) | 2004-05-21 | 2005-05-18 | Silicon structure |
| EP05745011A EP1747180A1 (en) | 2004-05-21 | 2005-05-18 | Silicon structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0411358A GB2414231A (en) | 2004-05-21 | 2004-05-21 | Porous silicon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0411358D0 GB0411358D0 (en) | 2004-06-23 |
| GB2414231A true GB2414231A (en) | 2005-11-23 |
Family
ID=32607728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0411358A Withdrawn GB2414231A (en) | 2004-05-21 | 2004-05-21 | Porous silicon |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1747180A1 (en) |
| JP (1) | JP2007537965A (en) |
| CA (1) | CA2564591A1 (en) |
| GB (1) | GB2414231A (en) |
| WO (1) | WO2005113467A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0601319D0 (en) | 2006-01-23 | 2006-03-01 | Imp Innovations Ltd | A method of fabricating pillars composed of silicon-based material |
| FR2915742B1 (en) * | 2007-05-04 | 2014-02-07 | Centre Nat Rech Scient | PROCESS FOR THE DELIVERY OF DIHYDROGEN FROM HYDROGENIC SILICON |
| GB0709165D0 (en) | 2007-05-11 | 2007-06-20 | Nexeon Ltd | A silicon anode for a rechargeable battery |
| GB0713898D0 (en) | 2007-07-17 | 2007-08-29 | Nexeon Ltd | A method of fabricating structured particles composed of silcon or a silicon-based material and their use in lithium rechargeable batteries |
| GB0713896D0 (en) | 2007-07-17 | 2007-08-29 | Nexeon Ltd | Method |
| GB0713895D0 (en) | 2007-07-17 | 2007-08-29 | Nexeon Ltd | Production |
| GB2464158B (en) | 2008-10-10 | 2011-04-20 | Nexeon Ltd | A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| GB2464157B (en) | 2008-10-10 | 2010-09-01 | Nexeon Ltd | A method of fabricating structured particles composed of silicon or a silicon-based material |
| GB2470056B (en) | 2009-05-07 | 2013-09-11 | Nexeon Ltd | A method of making silicon anode material for rechargeable cells |
| US9853292B2 (en) | 2009-05-11 | 2017-12-26 | Nexeon Limited | Electrode composition for a secondary battery cell |
| GB2470190B (en) | 2009-05-11 | 2011-07-13 | Nexeon Ltd | A binder for lithium ion rechargeable battery cells |
| GB201005979D0 (en) | 2010-04-09 | 2010-05-26 | Nexeon Ltd | A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries |
| GB201009519D0 (en) | 2010-06-07 | 2010-07-21 | Nexeon Ltd | An additive for lithium ion rechargeable battery cells |
| GB201014706D0 (en) | 2010-09-03 | 2010-10-20 | Nexeon Ltd | Porous electroactive material |
| GB201014707D0 (en) | 2010-09-03 | 2010-10-20 | Nexeon Ltd | Electroactive material |
| WO2012109459A1 (en) * | 2011-02-09 | 2012-08-16 | Hariharan Alleppey V | Recovery of silicon value from kerf silicon waste |
| GB2529409A (en) * | 2014-08-18 | 2016-02-24 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| EP3356308A4 (en) * | 2015-09-29 | 2019-07-31 | C-crete Technologies, LLC | Calcium-silicate-based porous particles, composition, method of making and use thereof |
| FR3075826B1 (en) * | 2017-12-22 | 2019-12-20 | Nanomakers | MANUFACTURING PROCESS INCORPORATING SILICON-BASED PARTICLES |
| JP2021042112A (en) * | 2019-09-13 | 2021-03-18 | 株式会社トクヤマ | Method for producing purified silicon fine particles |
| JP7464254B2 (en) | 2020-02-26 | 2024-04-09 | 国立大学法人広島大学 | Metallic materials and hydrogen production method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040848A (en) * | 1976-01-06 | 1977-08-09 | General Electric Company | Polycrystalline silicon articles containing boron by sintering |
| US4759887A (en) * | 1985-05-24 | 1988-07-26 | Heliotronic Forschungs- und Entwicklungs-gesellschaft fur Solarzellen-Grundstoffe mbH | Apparatus and process for the manufacture of shaped bodies from silicon granulates |
| US4767585A (en) * | 1986-04-23 | 1988-08-30 | Heliotronic Gmbh | Process for producing molded bodies from granular material of silicon, germanium or mixed crystals of these elements |
| JPH08109012A (en) * | 1994-10-11 | 1996-04-30 | Tonen Corp | Production of polycrystalline silicon plate |
| WO2001095952A1 (en) * | 2000-06-10 | 2001-12-20 | Psimedica Limited | A porous and/or polycrystalline silicon orthopaedic implant |
| WO2003101504A1 (en) * | 2002-05-31 | 2003-12-11 | Psimedica Limited | Orthopaedic scaffolds for tissue engineering |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3236276A1 (en) * | 1982-09-30 | 1984-04-05 | Heliotronic Forschungs- und Entwicklungsgesellschaft für Solarzellen-Grundstoffe mbH, 8263 Burghausen | NEW SILICON MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
| JPH01100010A (en) * | 1987-10-14 | 1989-04-18 | Canon Inc | Noncrystalline hydrogenated silicon fine particle film and production thereof |
| JP3259247B2 (en) * | 1993-03-11 | 2002-02-25 | 理化学研究所 | Porous silicon and method of manufacturing the same |
| GB9611437D0 (en) * | 1995-08-03 | 1996-08-07 | Secr Defence | Biomaterial |
| JPH11314911A (en) * | 1998-05-07 | 1999-11-16 | Sumitomo Sitix Amagasaki:Kk | Production of polycrystalline silicon ingot |
| WO2003106583A1 (en) * | 2002-06-18 | 2003-12-24 | 財団法人新産業創造研究機構 | Photosensitizer for generating singlet oxygen and method for generating singlet oxygen |
| FR2858313B1 (en) * | 2003-07-28 | 2005-12-16 | Centre Nat Rech Scient | HYDROGEN RESERVOIR BASED ON SILICON NANO STRUCTURES |
-
2004
- 2004-05-21 GB GB0411358A patent/GB2414231A/en not_active Withdrawn
-
2005
- 2005-05-18 EP EP05745011A patent/EP1747180A1/en not_active Withdrawn
- 2005-05-18 JP JP2007517409A patent/JP2007537965A/en active Pending
- 2005-05-18 CA CA002564591A patent/CA2564591A1/en not_active Abandoned
- 2005-05-18 WO PCT/GB2005/001910 patent/WO2005113467A1/en not_active Application Discontinuation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4040848A (en) * | 1976-01-06 | 1977-08-09 | General Electric Company | Polycrystalline silicon articles containing boron by sintering |
| US4759887A (en) * | 1985-05-24 | 1988-07-26 | Heliotronic Forschungs- und Entwicklungs-gesellschaft fur Solarzellen-Grundstoffe mbH | Apparatus and process for the manufacture of shaped bodies from silicon granulates |
| US4767585A (en) * | 1986-04-23 | 1988-08-30 | Heliotronic Gmbh | Process for producing molded bodies from granular material of silicon, germanium or mixed crystals of these elements |
| JPH08109012A (en) * | 1994-10-11 | 1996-04-30 | Tonen Corp | Production of polycrystalline silicon plate |
| WO2001095952A1 (en) * | 2000-06-10 | 2001-12-20 | Psimedica Limited | A porous and/or polycrystalline silicon orthopaedic implant |
| WO2003101504A1 (en) * | 2002-05-31 | 2003-12-11 | Psimedica Limited | Orthopaedic scaffolds for tissue engineering |
Non-Patent Citations (1)
| Title |
|---|
| WPI Abstract Accession No. 1996-263689 & JP 8109012 A (Tonen Corp) 30/04/1996 (see abstract) * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0411358D0 (en) | 2004-06-23 |
| EP1747180A1 (en) | 2007-01-31 |
| CA2564591A1 (en) | 2005-12-01 |
| WO2005113467A1 (en) | 2005-12-01 |
| JP2007537965A (en) | 2007-12-27 |
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