CA2645287C - Composite article and method - Google Patents

Composite article and method Download PDF

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Publication number
CA2645287C
CA2645287C CA2645287A CA2645287A CA2645287C CA 2645287 C CA2645287 C CA 2645287C CA 2645287 A CA2645287 A CA 2645287A CA 2645287 A CA2645287 A CA 2645287A CA 2645287 C CA2645287 C CA 2645287C
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article
zirconium
heating
titanium
heating step
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CA2645287A1 (en
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Gad Zak
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Richemont International SA
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MARIA DA COSTA DESIGN Inc
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Priority claimed from US12/272,675 external-priority patent/US8262814B2/en
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Priority to CA2645287A priority Critical patent/CA2645287C/en
Priority to IL202191A priority patent/IL202191A0/en
Publication of CA2645287A1 publication Critical patent/CA2645287A1/en
Priority to US13/440,938 priority patent/US9303306B2/en
Priority to US13/442,114 priority patent/US9382606B2/en
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Abstract

Method, and articles therefrom, for providing a hard, abrasion-resistant, attractive, oxide surface layer of selectable thickness and having an outer appearance within the scale from gray to blackness, to a zirconium titanium alloy article by heating the article in an oxygen containing atmosphere.

Description

COMPOSITE ARTICLE AND METHOD
FIELD OF THE INVENTION
[0001] The present invention relates to methods for forming a protective dark oxide layer or coating upon an article comprising zirconium, and to articles formed thereby.
More specifically, the invention relates to the formation of a protective dark oxide layer upon an article consisting of certain binary zirconium titanium alloys, and to the articles formed thereby.
BACKGROUND OF THE INVENTION
[0002] With the increase in civil use of what was considered during the "cold war" years as "strategic" or "restricted" metals, such as zirconium and titanium, and the relatively recent drop in their prices, an increasing number of consumer goods, medical, dental and orthopedic devices, civil engineering and architectural structural and decorative components, and other industrial as well as civil and military uses have been made of these metals and alloys thereof. With this increase in use, there has been a growing interest in the unique metallurgical properties of these metals and advantages as employed in known and new applications. These unique metallurgic properties include very high tensile and yield strength, light weight, and chemical inertness together with its corollary hypoallergenic property, which makes these metals and alloys suitable for dental, orthopedic and other prostheses such as joint replacements, arterial stents, and cardiac valves, as well as for consumer fashion accessories that benefit from the same properties, such as body-piercings, wrist watches, sunglass frames, and the like.
[0003] Increased interest in these metals and their uses has been accompanied by demand for methods for providing hardened surfaces, for providing surfaces exhibiting reduced friction, and for improving surface appearance. At the same time, their strength, low elasticity and ductility has rendered them materials suitable for night-stealth activities, from hunting to law enforcement and the military, for which dark colours are preferred, once a method for the generation and control of those colours and their shades of darkness is provided.
[0004] Anodizing is known for altering the colour and surface appearance of titanium and niobium. Anodizing of these metals and certain of their alloys generates a thin, colourful outer layer on the metal, which wears off readily and is easily scratched, chipped, or otherwise removed.
[0005] US Patent Number 6,093,259 to Watanabe et al. teaches methods for providing various coloured surfaces on titanium by treatment with aqueous alkaline solutions of KOH, NaOH and Li0H, applied singly or as a mixture, optionally accompanied by thermal treatment at moderate temperatures and optionally comprising a nitriding process.
[0006] US Patent Number 5,037,438 to Davidson, and US Patent Number 5,169,597 to Davidson et al., disclose surface treatment of another cold war metal, zirconium, by thermal or salt bath oxidation within temperature ranges readily achievable by conventional kilns, for improving mechanical and metallurgical properties. The resulting smooth and very hard blackened surface reportedly reduced friction, increased scratch resistance, enhanced the strength of the metal immediately beneath the surface coating and provided a blue/blackness coloured surface. These enhancements were attributed to oxygen diffusion into the substrate metal, which also improved the fatigue properties of the metal.
[0007] In attempting to produce articles that require or would benefit from the combination of high tensile strength, hardness, scratch and wear resistance, and colour control from dark gray to blackness, light weight, and hypoallergenicity, it is known that zirconium and titanium provide these benefits to varying degrees.
[0008] However, unalloyed titanium coloured according to the method taught by Watanabe et al. does not exhibit enhanced resistance to wear and generally retains the properties of untreated titanium. Also, the method requires the use of hazardous materials, personal safety equipment such as gas masks, impermeable gloves, complete skin coverage, and the like.
[0009] The use of unalloyed zirconium to the extent taught by Davidson is limited to unalloyed zirconium or alloys containing at least 80% zirconium, and preferably from about 95% to about 100%, by weight. In contrast, Davidson et al. teaches the use of a ternary alloy including niobium, adding cost and complexity compared to binary alloys.
Davidson and Davidson et al. are primarily directed to weight bearing prosthetic implants for which colour control is relatively unimportant.
[0010] While unalloyed zirconium displays high tensile strength, hypoallergenicity, and a beneficial surface coating when oxidized, it is known that alloys containing both zirconium and titanium offer superiour metallurgical properties compared to each metal alone. (See Yoshiaki, I. et al. "Improved Biocompatibility of Titanium-Zirconium (Ti-Zr) Alloy: Tissue Reaction and Sensitization to Ti-Zr Alloy Compared with Pure Ti and Zr in Rat Implantation" Mater. Trans. 46(10) : 2260-2267 (2005) (teaching superiour biocompatibility of Ti-Zr alloys compared to each metal alone)).
[0011] Certain ratio ranges of zirconium to titanium exhibit superiour mechanical properties compared to the component metals in the unalloyed state. (See Kobayashi, E.
"Mechanical properties of the binary titanium-zirconium alloys and their properties for biomedical purposes" J. Biomed Materials Research 29(8) (1995)). Alloys in the range of 1:1 zirconium to titanium by weight, disclosed for use as dental implants, exhibit hardness and tensile strength about 2.5 times as high as the unalloyed components. These results were reported for both cast and homogenized specimens.
[0012] Ternary alloys containing zirconium, titanium and a third metal are also known for applications including prostheses. US Patent Numbers 5,820,707 to Amick et al.
teaches ternary alloys including a third metal selected from niobium, tantalum and vanadium. The third metal is taught as passivating the tendency of the zirconium and titanium to ignite and combust. Amick et al. teaches very high temperatures and long duration for complete or near complete oxidation of the alloy workpiece which, therefore, requires passivation through the inclusion of the third metal in the alloy. The method reportedly provides smooth and hard surfaces which for some alloys are described as being "blue/blackness".
[0013] US Patent Number 6,759,134 to Rosenberg discloses ternary alloys containing titanium, niobium, and a third metal from the group consisting of zirconium, tantalum, molybdenum, hafnium, zirconium, chromium and mixtures thereof, with emphasis on alloys containing from 3% to 17% by weight niobium for its passivating properties and for the creation of a smooth and hard surface layer of niobium containing oxide with an aesthetic chromatic value.
[0014] However, Amick et al. and Rosenberg require at least a ternary alloy and do not teach control of the surface shade on a scale from dark gray to blackness. Amick et al. and Rosenberg also do not teach the benefits of enhanced tensile strength of the treated alloy.
[0015] In summary, Yoshiaki et al. and Kobayashi et al. teach binary zirconium titanium alloys of specified weight ratio that possess good metallurgical, mechanical and hypoallergenic properties. The ternary alloys of Amick et al. and Rosenberg are more intricate and costly to produce and have not been shown to possess the additional strength and hypoallergenic benefits of the binary alloy. Amick et al. furthermore, requires the application of very high temperatures requiring costlier equipment and production equipment, and/or longer process duration a parameter that adds to the costs too.
Davidson and Davidson et al. teach the benefits of zirconium based alloys comprising a zirconium oxide coating, focusing predominantly on very high zirconium contents in the alloys, and the suitability to certain prosthetic tasks, while Rosenberg and Amick et al. offer combinations that rely upon the presence of niobium oxide in the coating which form of the oxide was not shown to possess the same enhanced strength and fatigue resistance as the primarily zirconium oxide coating disclosed by Davidson
[0016] While the prior art provides a subset of the group of properties required by and benefiting various articles, namely, high tensile strength, high hardness, low ductility and elasticity, enhanced fatigue resistance, and biocompatability, the prior art does not teach the capability to combine the full scope of all of these benefits and the advantages in the capability to have controllable shades of dark gray to blackness nor does it offer the benefits of simplicity and cost reduction to be gained through the use of a binary alloy.
[0017] Therefore, there is a need in the art for alloys and surface coatings capable of providing articles exhibiting all of the potential beneficial properties available from zirconium titanium binary alloys. All this and more will become apparent to one of ordinary skill upon reading the following disclosure and claims.
SUMMARY OF THE INVENTION
[0018] The present invention is directed in one aspect to a method for overcoming the aforementioned disadvantages and limitations of the prior art by providing a method for darkening and hardening the surface of an article consisting of a binary zirconium titanium alloy of specified compositions. The inventor has found a synergistic combination, within articles produced by the method, of the metallurgical, mechanical, and hypoallergenic advantages of certain binary zirconium titanium alloys, combined with a hardened, darkened surface that resists abrasion, and has a colour from gray to blackness that is selectable according to the parameters of the method.
[0019] In a first aspect, a method having features of the present invention includes a step of providing an article consisting of between about 30.9% and about 65.6%
zirconium by atomic weight and titanium. Without limitation, the articles can be formed into their desired shapes by machining, casting, die forging, stamping, or the like. The articles may alternatively be formed by laser cut forming or hot isostatic pressing (HIP), both techniques known in the prior art. The articles optionally comprise a polished, satin, or matte finish, which influences the texture of the finished blackened surface. The method further comprises heating the article in an oxygen containing atmosphere at a temperature of between about 250 and about 880 degrees Celsius for between about 10 and about 110 minutes to produce the hardened, darkened surface. In certain preferred aspects, the alloy consists of between about 34.4% and about 65.6%
zirconium by atomic weight.
[0020] In a second aspect, a method having features of the present invention includes a step of providing an article consisting of between about 18.496% and about 30.9%
zirconium by atomic weight and titanium. The method further comprises heating the article in an oxygen containing atmosphere in a first heating step and a second heating step with a quenching step interposed, the heating steps being performed at a temperature of between about 250 and about 880 degrees Celsius for a total duration of between about 10 and about 110 minutes to produce the hardened, darkened surface. Optionally, the first heating step is performed at a lower temperature than said second heating step. For example, and without limitation, in certain embodiments, the first heating step is carried out at a temperature of between about 250 and about 480 degrees Celsius for between about 10 and about 40 minutes, and the second heating step is carried out at a temperature of between about 480 and about 880 degrees Celsius for between about 10 and about 70 minutes.
[0021] In certain embodiments, the oxygen containing atmosphere is air.
[0022] In another aspect, an article having features according to the present invention comprises zirconium titanium binary alloy article consisting of between about 30.9% and about 65.6%
zirconium by atomic weight and titanium further comprising a darkened oxide containing surface or portion thereof produced according to one of the foregoing methods.

4193637 vi
[0023] In certain preferred aspects, the article consists of between about 34.4% and about 65.6%
zirconium by atomic weight.
[0024] In another aspect, an article having features according to the present invention -5a-4193637 vi comprises zirconium titanium binary alloy artide consisting of between about 18.4% and about 30.9% zirconium by atomic weight and titanium further comprising a darkened oxide containing surface or portion thereof produced according to one of the foregoing methods.
[0025] It is therefore an object of the present invention to provide articles that require or benefit from any combination of properties from within the group comprising, without limitation, high tensile strength, high hardness, resistance to fatigue or wear or scratch, low ductility and elasticity, hypoallergenicity, and shades of gray and blackness.
Heating duration may be extended for larger articles.
[0026] It is a further object of the invention to provide articles comprising an aesthetic outer surface or coating that exhibits shades from gray to blackness.
[0027] It is a further object of the invention to provide articles comprising a darkened surface suitable for stealth goods, hunting and sporting equipment, and body adornments that are night stealthy such as a soldier's bracelet or ring.
[0028] It is a further object of the invention to provide a ceramic-like coating that exhibits low wear and low friction suitable for articles requiring extended periods of mechanical contact, such as for example butterfly valves.
[0029] It is a further object of the invention to provide a matte or satin coating that has low reflectivity and is suitable for nighttime stealth articles.
[0030] These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows a cross-section of an article according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0031] The composition of binary zirconium titanium alloys in the present disclosure are expressed by atomic weight ratio, in part to draw attention to the possibility of using unalloyed titanium and zirconium in preparing the alloys according to the present invention, despite the market's offerings of various popular alloys of titanium and zirconium. To convert from atomic weight ratio to actual weight ratio, the product of a selected element's atomic weight and its atomic weight ratio in percentage is divided by the sum of such products for the alloy constituents. For example, a ratio of 34.42% zirconium to 65.58% titanium by atomic weight, given an atomic weight for Ti of 47.867 and an atomic weight for Zr of 91.224, provides the following for the titanium ratio by weight:
(47.867 x 65.58%) : (47.867 x 65.58% + 91.224 x 34.42%) x 100 =
49.99%
[0032] The binary zirconium titanium alloys for use in the methods and articles according to the present invention consist of between about 18.4% and about 65.6% zirconium by atomic weight and titanium. Trace amounts of impurities, including other metals, may be present to an art-recognized degree. Certain alloys for use in the present invention can be purchased from any of several metal alloy-producing mills producing zirconium titanium alloys worldwide, and in particular in North America, and in Central and Eastern Europe.
[0033] In preferred embodiments, a binary alloy consisting of from about 65.58% titanium by atomic weight (about 50% by weight) and about 34.42% zirconium by atomic weight (about 50%
by weight) is used, or alloys are used that fall within about 4% of these values. Kobayashi et al.
(supra) teaches superior strength and hardness, up to 2.5 fold, of these alloys compared to pure zirconium and titanium.
[00341 The articles of the present invention can be made by any means known in the art for shaping zirconium titanium alloys, including without limitation machining, casting, stamping, or die-forging. Laser cut forming or hot isostatic pressing (HIP), both known in the prior art, may alternatively be used. It is known that certain compositions of zirconium titanium alloys are ignitable (see, e.g. US Patent No. 5,820,707 to Amick et al.) and highly reactive so due care must be taken when working such alloys. Machining requires precautionary measures as are known in the art, including but not limited to slow speeds and liberal lubrication and cooling.
Likewise, opening of a casting investment must be performed only after complete cooling.
[00351 The article is heated, preferably by heating in a kiln providing an oxygen containing ambient gas, to within the range of about 250 degrees Celsius to about 880 degrees Celsius. In certain embodiments, a single heating step is provided comprising a duration of from 4193638 vi about 10 to about 110 minutes, followed by air cooling, water quenching, or the like.
[0036] The inventor has found that with an increased gas supply, oxidation proceeds more rapidly but is accompanied by an increased risk of combustion. In preferred embodiments, a kiln is selected to have a moderate and unforced air supply in the range of 4 to 6 square inches per cubic foot of kiln volume.
[0037] Preferably, two heating steps are used, with a quenching step such as a water or air quenching interposed between the heating steps. The temperature and duration of heating are selected to provide a strongly adherent oxide-rich layer with the desired shade from gray to blackness and sufficient wear resistance. Outer layers or coatings having a darker appearance exhibit excellent resistance to wear and penetrate somewhat deeper into the substrate alloy. Where the surface of the article to be treated is polished, a smooth coating is obtained that is sufficiently hard and wear resistant to be particularly suited for uses involving frequent sliding contact with other surfaces, or impacts, or the like. Articles to be treated that have a brushed surface texture provide lighter shades.
[0038] Referring now to FIG. 1, there is shown an article according to the present invention comprising a zirconium titanium alloy 100 and a darkened surface 102.
[0039] Most preferably, a first heating step at a lower temperature is followed by a second heating step, with a quenching step interposed between the two. This process has been found beneficial to reduce ignition risk. In preferred embodiments, a first heating step can comprise heating to between about 250 degrees Celsius to about 480 degrees Celsius for between about 10 to about 40 minutes. Following an optional quenching step, a second heating step can be performed by heating to between about 480 degrees Celsius to about 880 degrees Celsius for up to about 100 minutes or until a predetermined gray tone or degree of blacknessness is obtained.
[0040] Not to be thereby limited by theory, the thermal treatment of the present invention provides an oxide layer that is believed to comprise a high proportion of zirconium oxide and to further harden and strengthen the metal by the diffusion of oxygen within the partially oxidized surface layer, and in the deeper alloy substrate to which it is adherent. In embodiments comprising two heating steps, it is believed that a thicker final oxide layer is formed due to the possibility that oxygen penetrates more deeply into the substrate metal during a first, lower temperature, step than it does if exposed to an initial higher temperature that produces a more rapid thickening of the oxide layer.
[0041] Articles treated according to the method of the present invention are less susceptible to subsequent ignition. Exposure of treated samples to direct flame in the range of 1,300 to 1,400 degrees Celsius for up to ten minutes failed to combust or undergo further oxidation.
This property usefully extends the range of applications of the present invention to include, for example, firearm parts, subject to proper testing and certification.
EXAMPLES
[0042] Alloys for use in the method and article of the present invention are exemplified in TABLE 1:

ALLOY Zr by atomic wt. % Ti by atomic wt.
34.42 65.58 II 33.52 66.48 III 30.89 69.11 IV 40.05 59.95 V 67.37 32.63 [0043] In TABLE 2, it is demonstrated that the duration and temperature of thermal treatment can be adjusted to control the resulting shade of gray or blacknessness in the resulting article. A darker surface is obtained with longer and/or hotter treatment, while a lighter gray finish is obtained at lower temperatures and/or shorter duration.
[0044] Results obtained with the present invention are compared in TABLE 2 with unalloyed zirconium (Zr702) and a zirconium alloy with low levels (2-3%) of niobium (Zr705).

(Formation of a darkened, hardened coating according to the method of the present invention.) Alloy 1st cycle 1st cycle 2nd cycle 2nd cycle Resulting (min) (C) (min) (C) surface*
1 II 25 250 50 750 Dark blacknessness, smooth*
2 VI 35 250 35 680 Medium blacknessness, smooth*
3 II 30 350 30 725 Pitch blackness, smooth*
4 VI 40 650 Light blacknessness, smooth*
5 II 65 600 Medium blacknessness, matte 6 VI 30 250 80 480 Medium gray, smooth*
7 II 25 650 Medium charcoal gray, smooth*
8 VI 13 880 Light to mediumcharcoal gray, smooth*
9 11 880 Light to o medium gray, smooth*
10 Zr702 35 620 Medium charcoal, matte 11 Zr702 70 700 Pitch blackness, smooth*
12 Zr705 40 650 Light charcoal, matte 13 Zr702 25 300 26 600 Medium to dark charcoal, matte *articles polished prior to treatment [0045] In a further example, a night-stealth automotive and/or stealth automotive hubcap is provided. The hubcap is cast into the desired shape and provided with a satin-like low-polish. The hubcap is then heated to within the range of 250 to 350 degrees for from 10 to 40 minutes. Next, the hubcap is heated by the same method for 20 to 40 minutes at 600 to 700 degrees Celsius. The hubcap is from charcoal gray to blacknessness in appearance and has a matte, wear resistant surface.
[0046] In use, the method of the present invention is used to produce articles that are also encompassed by the present invention. The articles can be any article consisting of zirconium titanium alloy within the composition range of the present invention that requires or may benefit from a hard, tough, gray to blackness outer surface layer.
Without limitation, articles within the scope of the present invention can include articles that comprise pivoting or swiveling parts such as revolving disk and butterfly valves, cardiac valves, and valves for liquids and gases. In these applications, the swiveling parts can be springingly retained about their axis by insertion under tensile stress between mounting points, or more loosely retained. Other article embodiments can include dental implants and medical prostheses such as joint and bone replacements. Further, the present invention can provide a tough and attractive outer surface to sporting goods such as golf clubs, durable and night-stealth hunting goods such as knives, outdoor equipment such as binocular outer casings, bow coatings, water canteens, field-compasses and the like. The articles according to the present invention can be stealth items such as for law enforcement and armed forces, such as helmets, buckles, ID tags, night vision equipment, laptop and communications and data storage equipment casings, firearms and parts thereof such as sights, triggers, cartridges, magazines, barrels, and the like. Other articles within the scope of the present invention are night-stealth compatible jewellery items of low wear, for use by armed forces and law enforcement personnel, for example bands including bands that benefit from the invention's metallurgical attributes of excellent strength, tensile strength, low elasticity and ductility, and, therefore, strong springiness, wherein a stone may be set under pressure and retained between two connected portions of the band. Such stealth compatible and low wear jewellery items can further comprise wedding bands, buckles, bracelets, chains, earrings, watches, chains, sunglass frames, cuff links, tie-pins, money or document clips, bracelets and necklaces. The darkened surface of jewellery according to the present invention can provide an aesthetic and/or a utilitarian function. Yet further, marine and/or night-stealth marine items such as boat masts, deck handles, steering wheels, throttles; automotive and/or stealth automotive parts such as gearshift levers, hubcaps, steering wheels; and household items such as door handles, cabinet handles, keys, cutlery, faucets, light fixtures and kitchen implements can all be provided within the scope of the present invention. Yet further examples can include musical instruments, such as brass instruments with valves, for which the hypoallergenic and excellent wear resisting properties of the present invention are well suited. Still further examples include architectural structural and surface materials for which a darkened surface prepared according to the method of the present invention can be used to alter the structural and surface material thermal properties and the lightness of the alloy.

Claims (14)

What is claimed is:
1. A method of making a metallic article of zirconium and titanium alloys, benefiting from the hardness, tensile strength, ductility and elasticity of a zirconium-titanium alloy system, having, further, a hardened surface which is hypo-allergenic, wear resistant, and having a monochromatic colour within the scale of grey to blackness comprising the steps of:
(a) combining zirconium and titanium to create a binary zirconium and titanium alloy combination of between 18.4% to 30.8% or 40.1% to 65.6%
zirconium by atomic weight and titanium;
(b ) forming the binary zirconium and titanium alloy combination into a desired shape through machining, casting, die forging, stamping, laser cut forming, or hot isostatic pressing to form an unfinished metallic article; and (c) heating the unfinished metallic article in an oxygen containing ambient gas supplied at a controlled flow rate at a temperature range between 250 and 880 degrees Celsius and for a time period of between 10 to 110 minutes;
wherein the combination of heating temperature and heating duration is determined by the desired monochromatic colour of the metallic article within the scale of grey to blackness, whereby selection of a first temperature and heating cycle of a first duration produces an oxide layer having a colour at the grey end of the scale and selection of at least one of a second temperature, greater than the first temperature, and heating cycle of a second duration, greater than the first duration, produces an oxide layer having a colour at the blackness end of the scale.
2. The method of Claim 1, further comprising a quenching step after the step of heating the unfinished metallic article.
3. The method of Claim 1 or Claim 2, wherein the heating step is divided into a first heating step and a second heating step.
4. The method of Claim 3, further comprising a quenching step interposed between the first heating step and the second heating step.
5. The method of Claim 3 or Claim 4, wherein said first heating step is performed at a lower temperature than said second heating step.
6. The method of Claim 5, wherein the first heating step is carried out at a temperature of between about 250 and about 480 degrees Celsius for between about 10 and about 40 minutes.
7. The method of Claim 5, wherein the second heating step is carried out at a temperature of between about 480 and about 880 degrees Celsius for between about 10 and about 70 minutes.
8. The method of Claim 1, wherein said oxygen containing ambient gas is air.
9. A zirconium titanium binary alloy article comprising a darkened surface or portion thereof produced according to the method of any one of Claims 1 to 8.
10. The article of Claim 9, wherein the article is selected from the group consisting of a prosthesis, sports equipment, a golf club, hunting equipment, camping equipment, binocular encasement, an encasement for portable telecommunications, an encasement for telecommunications, an encasement for an information storage device, and firearm parts and barrels.
11. The article of Claim 9, wherein the article is a stealth good.
12. The article of Claim 9, wherein the article comprises swiveling parts.
13. The article of Claim 9, wherein the article comprises a musical instrument.
14. The article of Claim 9, wherein the article comprises an architectural structural or surface material.
CA2645287A 2007-11-15 2008-11-27 Composite article and method Active CA2645287C (en)

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Application Number Priority Date Filing Date Title
CA2645287A CA2645287C (en) 2008-11-17 2008-11-27 Composite article and method
IL202191A IL202191A0 (en) 2008-11-17 2009-11-17 Composite article and method
US13/440,938 US9303306B2 (en) 2007-11-15 2012-04-05 Composite article and method
US13/442,114 US9382606B2 (en) 2007-11-16 2012-04-09 Composite article and method

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US12/272,675 2008-11-17
US12/272,675 US8262814B2 (en) 2007-11-15 2008-11-17 Composite article and method
CA2645287A CA2645287C (en) 2008-11-17 2008-11-27 Composite article and method

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