AU656647B2

AU656647B2 - Aluminum with controlled oxidation

Info

Publication number: AU656647B2
Application number: AU30734/92A
Authority: AU
Inventors: Joseph Kustanovich
Original assignee: Shirat Enterprises Ltd
Current assignee: GOLDMUNTZ LAWRENCE; Shirat Enterprises Ltd
Priority date: 1991-11-11
Filing date: 1992-11-09
Publication date: 1995-02-09
Anticipated expiration: 2012-11-09
Also published as: JPH09509983A; EP0612283A1; DE612283T1; AU3073492A; AU1793695A; EP0612283A4; IL100022A0; WO1993009946A1

Description

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m--;rl OPI DATE 15/06/93 APPLN. ID 30734/92 IIl l l lilllllIll1 AOJP DATE 19/08/93 PCT NUMBER PCT/US92/09727 1111111111111111 I II 11111111111 I 111111 AU9230734 IN I KNA IUNAL APPLICAIION PUBLISHED UN'.)ER THE PATENT COOPERATION TREATY PCT) (51) International Patent Classification 5 B32B 15/08, A61K 9/00 90/04 Al (11) International Publication Number: (43) International Publication Date: WO 93/09946 27 May 1993 (7.05.93 27 Mav 1993 7.05.93) 1 (21) International Application Number: (22) International Filing Date: 9 Priority data: 100022 11 Noven PCT/US92/09727 November 1992 (09.11.92) nber 1991 (11.11.91) IL (81) Designated States: AT, AU, BB, BG, BR, CA, CH. CS.

DE, DK, ES, FI, GB, HU, JP. KP, KR, LK. LU, MG.

MN, MW, NL, NO, PL, RO, RU. SD, SE. European patent (AT, BE, CH, DE, DK, ES, FR, GB. GR. IE. IT.

LU, MC, NL, SE), OAPI patent (BF. BJ. CF. CG. CI.

CM, GA, GN, ML, MR, SN, TD, TG).

Published With international search report.

Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt of amendments.

(71) Applicants: SHIRAT ENTERPRISES LTD. [1L/IL]; 2 Ibn Gviro Street, 64 077 Tel Aviv GOLDMUNTZ, Lawrence [US/US]; 29 Kalorama Circle, Washington, DC 20008 (US).

(72) Inventor: KUSTANOVICH, Joseph 32A Eisenberg Street, 76 288 Rehovot (IL).

(74) Agents: FRIEDMAN, Mark, M. et al.; Benjamin J. Barish Co., c/o Victoria Sheinbein. 2940 Birchtree Lane, Silver Spring. MD 20906 (US).

(54) Title: ALUMINUM WITH CONTROLLED OXIDATION 6 82 92 94 (57) Abstract An aluminurm which includes dopant in an amount which is effective in providing controlled oxidation of the aluminum in the presence of oxygen, thereby preventing the formation of an oxidation-resistant aluminum oxide layer (96) on the aluminum.

The aluminum can be incorporated in a flexible laminar sheet material, which, in turn, can be used as a packaging material ~e -e I WO 93/09946 PCT/US92/0972 7 ALUMINUM WITH CONTROLLED OXIDATIO:: FIELD AND BACKGROUND OF THE INVENTION The present invention relates to aluminum with controlled oxidation, doped aluminum foil, flexible laminar sheet material comprising doped aluminum, as well as articles of commerce characterized by being packaged with such doped foil, or with such flexible laminar sheet material.

Aluminum metal is characterized by the ready formation in air of a durable surface oxide layer, which is. generally effective in preventing further oxidation of the surface. This characteristic of aluminum is generally accepted as an advantage in many applications.

Moreover, aluminum foil, and supported aluminum film, are popular packaging materials due to their cheapness, non-toxic properties, ease of working and of forming laminates with polymeric films, attractive reflective metallic appearance and durability. Their durability is in turn due in part to innate mechanical strength, and in part due to the fact that the aluminum foil or film readily forms a degradation-resistan initial surface cide layer, as mentioned above.

Many articles and products of commerce are susceptible to oxidative degradation in storage, either by direct chemical action of oxygen or by bacterial processes in which the presence of oxygen is essential.

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WO 93/09946 PCr/US92/0972" Methods have been developed "or the protection of' such oxidation-susceptible articles or products from oxidative degradation, such as packaging in an inert atmosphere; hermetic sealing, e.g. with heavy or laminated polymeric films; including oxygen absorbents in the packaging or in the product; or including antioxidants, e.g. in foodstuffs or medical products.

As mentioned above, the durable nature of aluminum foil or film as a ?ackaging material is at least in part due to the fact that it undergoes an initial oxidation reaction to produce a surface oxide layer which is resistant to degradation and .particularly to any further oxidation. It has surprisingly been found in accordance with the present invention, however, that there is a considerable advantage is sacrificing, at least, to some extent, the durability of aluminum by making it controllably more susceptible to oxidation, so that it can prolong the shelflife of oxidation-susceptible articles or products, by reacting with and therefore removing oxygen from the environment of' such packaged commercial articles or products.

Persons skilled in the. art will appreciate that Aaluminum foil or film packaging material in general has a much greater shelf-life than the packaged article or product; thus it will be acceptable to reduce somewhat the shelf-life of such packaging material, if simultaneously the shelf-life of the packaged article or product is extended because it is thus protected from the deleterious effects of oxygen in its immediate environment. Reduction of the shelf-life of the aluminum foil or film functionin- effectively as antioxidant can of course be 2p SUBSTITUTE SHEET WO 93/09946 PCr/US92/09727 countered by laminating i;t with a polymeric layer or layers which will maintain the integrity of the wrapping material even if the foil layer deteriorates.

The use of packaging comprising aluminum foil in the effective role of oxygen-reactant or antioxidant possesses the following advantages: the necessary technology, tools and experience for producing aluminum foil, or polymer -film -laminated with aluminum already exists and is very widely accepted; aluminum has a very high capacity for reaction with oxygen; thus, 1 g. aluminum has the potential capacity to remove all the oxygen from 3 1. air at N. T.P.; when in accordance with the invention aluminum foil is doped to render it susceptible to continuous oxidation.

i. e. oxidation is not halted after initial oxidation of the aluminum surface, oxidation of the foil will continue until all free oxygen within the packaged environment has been removed; the aluminum oxide produced is chemically inert and non-toxic; -when the protected product is used for human consumption, the doping material can be readily selected so as to be also non-toxic; the invention possesses an environmental advantage, because it replaces (for example) durable aluminum cans, wrappings and bottle tops with aluminum which may be made completely degradable in the atmosphere to aluminum oxide which would readily disperse and in effect become virtually invisible.

3 SUBSTITUTE SHEET r- 7 1WO 93/09946 PCT/L'S92/0972" SUMM4ARY OF THE INVETION The present invenvtion accordingly provides in one aspect, aluminum which comprises dopant in an amount effective to provide controlled oxidation of the aluminum in presence of oxygen, and thereby to prevent formation of an oxidationresistant aluminum oxide layer on the aluminum.

In another aspect, the invention provides aluminum foil or f ilm doped with at least one metal selected from lithium, sodlium, potassium, rulbidium, caesium, beryllium, magnesium, calcium, strontium and bazium. Persons skilled in the art will appreciate the necessity for excluding such of the dopant metals as are toxic beryllium) when the doped foil or film of' the invention is intended for-use zh 'products, e.g. .foods tuf fs intended for human use; on the other hand there may be applications where the use of relatively toxic dopants may possibly be tolerated, e.g. to remove oxygen from a sealed chemical react~ion vessel..

The invention moreover provides in another aspect, a flexible laminar sheet material which comprises doped aluminum foil or film as just described, having a polymeric layer (which in one embodiment may be a breathable layer) on one side thereof.

In yet another aspect, the invention provides a flexible laminar sheet m~aterial which comprises doped aluminum as defined above having a polymeric layer on each side thereof; *in this aspect of the invention, the polymeric layer on at least one SUBSTITUTE

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u I 1 C WO 93/09946 PCT/US92/09727 side (and if desired on each side) of the doped alumint l foil may be a breathable polymeric layer.

In still another aspect, the invention provides a flexible laminar sheet material which comprises a polymeric film having on one side thereof at least one layer of doped aluminum, wherein the doped aluminum has been doped with a dopant comprisingat least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium; the above remarks concerning the avoidance of relatively toxic dopants for certain applications should be noted. In one embodiment of this aspect of the invention, the polymeric film has on one side thereof a single layer of doped aluminum. In another embodiment, the polymeric film has on one side thereof at least two layers of aluminum and at least the layer of aluminum remote from said polymeric film is a doped aluminum layer; there may be one one side of the polymeric film an undoped aluminum layer and superimposed thereon a doped aluminum layer.

The flexible laminar sheet material described in the preceding paragraph may comprise additionally a breathable polymeric layer superimposed on the at least one doped aluminum layer, the breathable polymeric layer being the outermost layer remote from said polymeric film.

In yet another aspect, the invention provides a packaged article of commerce which is characterized by at least one of the the following features, namely: SUBSTITUTE' SHEET -u WO 93/09946 PCTIUS92/09727 at least part of the packaging comprises at least one material selected from doped aluminum foil and flexible lamiLnar sheet material, according- to the present invention as defined herein; it contains internally, doped aluminum as defined herein other than in the form of packaging material, thereby serving to remove oxygen (by reaction therewith) from the internal space of the package.

For purposes- of definition, -the term "article of commerce" in the present specification and cl aims is intended to include not only coherent articles, but also manufactured products such as chemical and medicinal substances, e.g. drugs, and comestibles or foodstuffs, which may exist and be marketed in substantially non-coherent form.

The present invention provides for the possibility of incorporating an amount of dopant in aluminum, packaging materials, which is adequate to promote the eventual conversion of all the aluminum to aluminura oxide, on prolonged exposure to air. This of course constitutes a considerable ecological advantage of the invention, since it would potentially avoid lUttering the countryside with long-lasting expended aluminum packaging.

BRIEF DESCRIPION OF THE DRAWINGS Fig. 1 illustrates a method for producing an embodiment of doped aluminum materials in accordance with the present invention.

Fig. 2A illustrates schematically kn~own apparatus for 6 sIJBsTITUTM SHMC:7 a

A

WO 93/09946 PCT/US92/09727 coating polymeric film with aluminum by evaporation in vacuum.

Fig. 2B illustrates the adaptation of the high vacuum chamber of Fig. 2A for the purpose of producing an embodiment of doped aluminum materials in accordance with the invention.

Fig. 2C illustrates a modification of the rpparatus of Fig. 2B, for the purpose of producing a different embodiment of I doped aluminum materials in accordance with the invention.

Fig. 3A illustrates schematically an embodiment of a laminate according to-the invention which may be produced using the apparatus of Fig. 2C.

Fig. 3B illustrates schematically an embodiment of a laminate according to the invention different from the embodiment of Fig. 3A.

Figs. 4A and 4B illustrate a package utilizing doped aluminum in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION While, in general, the doping ingredient in accordance with the invention may be preferably selected from among lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium, persons skilled in the art will be aware that a narrower selection will be necessary where the protected product is e.g. a foodstuff or medicament intended for human consumption, so that toxic materials are not introduced.

Without prejudice to the generality of the invention, the presently preferred doping metal is calcium. Calcium is the basis of many compounds essential to life and will obviously give rise to non-toxic products; moreover, it is on the one hand SUBSTITUTE S

T

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WO 93/09946 PC1'/US92/09727 sufficiently active to provide controlled oxidation and thus prevent the formation of a hard aluminum oxide layer which prevents further reaction, while on the other hand, its moderate activity in this respect is such as to obviate the necessity for developing new technologies for producing the al~uminum foil- or film-based packaging matrriaJ.

In the flexible laminar sheet materi.al of the invention, the undoped al~uminum ayer anu-d the aluminum layers comprising dopant, and/or the dopant itself, may be deposited on the polymeric film by any method kn~own to persons skilled in the art. However, it is presently preferred to effect deposition of at least one of the following materials, namely said aluminum and said dopant, by evaporation in vacuum.

Fi g. 1 depicts schematically a laboratory arrangement of items in the space 10 of a high %acuum chamber which the boundaries are not shown, for producing doped aluminum materials in accordance with the present invention. Evaporation vessels 2- 14 ,contain respectively aluminum and calcium -(or other doping metals in accordance with the invention) which are evaporated by reLspective heaters 6, 8, which may be e.g. resistance heaters.

The depicted arrangement may be pL.. t of an Edwards (trademark) 306 coating system. The high vacuum may be of the order of e.g.

106millibar. The support 12 may be glass, polyethylene or polypropylene. In the course of evaporation, a film of doped aluminum collects on the underside of the support at 14. It may be determined that the amount of each metal deposited at 14 is a 8 SUBSTITUTE SHEET WO 93/0"46 WO 93O99MiPCT/US92/09727 junction of' the current applied to heaters 6 and 8, over a fi-ted time neriod, such as 40 seconds. Subsequently, the appropriate current may be applied to each heater in order that the different metals deposit simultaneously on support 12 in the desired proportions.

After preparation in this manner, samples were exposed to room temperature and atmospheric pressure until oxidation was complete. The inverse of' the time for complete oxidation was used as a measure of' the rate of' oxidation; this rate-was found to be approximately proportional to the dopant concentration at concentrations of' up to a few atomic percent. At these concentrations, it was found that a polymeric film coated with doped aluminum containing Ca:Al in a weight ratio of' 5:100 reduced the concentratiLon of' jgen from an initial to less A than 0.01,' after 4 days at room temperature, when tested in a closed glass vessel of' 120 ml. capacity.

Fig. 2A depicts schematically' known apparatus for coating polymeric film as it is unwound from bobbin 22 which rotates in an anticlockw3.se direction about axle 24 and simultaneously wound onto bobbin 26 as it rotates anticiockwise about axle 28. Bobbins 22, 26 are located in respective vacuum chambers 30. 32, the polymeric film passing into high vacuum chamber 34 through opening 38 and exiting from high vacuum chamber 34 via opening 40. The polymeric film is coated with aluminum by evaporation from vessel 36, heated by resistance heater 42.

SUBSTITUTE SHEET WO 93/09946 PC1'/US92/09727 Fig. 2B (in which reference numerals repeated from Fig.

2A have the same meaning as before) shows the adaptation of high vacuum chamber 314, of the apparatus described with reference to Fig. 2A, for purposes of the present invention by inserting additionally therein an evaporation vessel for evaporation of dopant onto the polymeric film 20 by use of resistance heater 46.

The thickniess of the aluminum layer is controlled by the temperature of heater 42 and the percentage of dopeant therein will be controlled -by--the temperature of -resistance heater 46.

It will be appreciated that the product in the f orm of a wound roll of doped aluminum film on a polymer-ic film support i.s protected against oxidation in storage by superimposed windings of the same doped aluminum/polymer laminate, and that the outer layer may be protected from oxidation by a tightly wound wrapping impervious to air.

In the modification of Fig. 2.B depicted in Fig. 2C, the two evaporation vessels 36, 144, with respective heaters 42, 46, are spaced apart and partially separated by screen 148 which i.

effective to enable a mixture of aluminum and dopant in preselected proportions to be superimposed on an initial aluminum layer deposited on film 20, insofar as under vacuum the dopant particles (as also the aluminum particles) travel substantially linearly from the evaporation vessels to film 20. A consequence of the arrangement depicted in Fig. 2C is that a thin layer of the deposited aluminum film remote from the evaporation vessels will be dapant free and thus protect the aluminum film from oxidation at that remote surface, as well as enhancing the decorative appearance of the product.

SUBSTITUTE SHEET WO 93/09946 PCT/US92/09727 The product of the process shown in Fig. 2C is schematically depicted in Fig. 3A and consists of a laminate of polymeric film 62/undoped aluminum film 64/doped al~uminum film 66. The product 60 as described with reference to Fig. 3A may be subsequently laminated by kn~own means with a further, e.g.

breathable, polymeric film, thereby to obtain the laminar product schematically depicted in Fig. 3B, which consists of polymeric film 62/undoped aluminum film 64/doped aluminum film 66/breathable polymeric film 72, the breathable layer 72 preventing direct contact of the doped aluminum layer with the protected packaged product, yet nevertheless permitting reaction of the doped aluminum layer with oxygen.

Figures 4A and 1 4B illustrate a packaged article in the invention. In both figures, a plastic container 80 is sealed by iaminar. foil 82, comprisiLng a doped aluminum layer in accordance with the present invention, along outwardly turned flange 84~ which is integral with container 80. When access to the contents is desired, the laminar foil may be at least partly removed from, front left corner 86 of the foil. In Fig. 4A, the packaged article, which may contain for example foodstuffs -suc h as soft cheese or haJlva, is shown before opening, and neither the contents nor the laminar structure of the foil are shown in this figure.

4B shows the iiow partly opened package of Fig. 4A, the opening having been achieved by the well kniown method of cutting the foil at the top front-left corner of' the container SUBSTITUTE SHEET I WO 93/09946 PCT/US92/09727 and pulling the foil away from this corner to reveal foodstuff (or other content) 88. In Fig. 42, the thickniess of the foil is shown greatly enlarged in order to depict its lamiLna~r structure. Illustrated in this figure is a four-layer laminate in which the outer layer is a polymeric protective film 92 which is in contact with a deposited undoped aluminum layer 94, fo)llowed by a doped al.uminum layer 96 and an inner breathable polymeric layer 98.

When the container 80 is originally sealed by foil 82, any oxygen which may be in the interior of the pac-kage will diffuse through breathable layer 98 and reacted with the doped alumiLnum layer 96, thus inhibiting oxidative deterioration of the contents.

It will be appreciated that the same principle applies when the whole of, rather than part of, the container is in the nature of a foil, e.g. in t!,e case of potato chips or some readyto-cook meals. It will further be appreciate~d 'that the mentioned foodstuffs are only illustrative as to the contents ,of the package, which could of' course alternatively contain other foodstuffs, or non-foodstuffs such as pharmaceutical compositions.

The laminate could also of course differ from that illustrated in Fig. 4BE, e.g. a single doped aluminum layer could replace layers 94 and 96. Alternatively, the four-layer laminate may be replaced by an aluminum foil, doped in accordance with the invention on the inside surface only, i.e. on the surface nearest 12 SUBSTITUTE SHEET WO 93/09946 PCr/US92/09727 to the contents of the package; such foil may optionally have a breathable polymeric layer between the doped aluminum surface and the contents of the package.

In another embodiment, not illustrated, foil 90 may be replaced by a conventional foil sealant, and antioxidative protection of the contents of the package may be achieved by insertion into the package before sealing of a piece of aluminum (doped in accordance..with the invention) if desired encased in breathable polymer.

Persons skilled in the art will be a,;are of the manner in which the processes described with reference to the Figures may be adapted to the doping of aluminum foil rather than the simultaneous deposition of aluminum and dopant as has been described. Polymeric film may also be interleaved with the doped foil so as to protect it prior to use. Alternatively doped I aluminum foil could be manufactured by cold or hot rolling, but it will be appreciated that hot doped sheets or liquid aluminum containing dopant, will need to be protected from oxidation by working in an inert gas atmosphere in substantial 'absence of oxygen.

APPLICATIONS OF THE INVENTION It is contemplated that doped aluminum foil and the flexible laminar sheet materials (incorporated doped a.3.uinum film or foil) according to the invention will be useful in the packaging of products such as foods, medicaments, cosmetics and semiconductors (for example), which are sensitive to direct 13 SUBSTITUTE SHEET WO 93/09946 PCr/US92/09727 chemical oxidation and/or bacterial deterioration in presence of' oxygen. The potential ecological advantage of aluminum packaging which after use and in the course of time is capable of complete conversion to oxide, has already been mentioned.

A particular application of' the invention is to dairy and meat products, which often spoil rapidly as a result of oxidation of their fat content and bacterial deterioration; such products may be packea using as packaging, the materials of the invention including doped aluminum, such that oxygen contained within the packet would react with the doped aluminum. Baked goods may be similarly wrapped. It is further contemplated that the materials of' the invention may readily be printed as other aluminum foils, films an-d polymeric laminates. Caps containing an internal surface including doped aluminum, e.g. laminated with breathable polymeric film, could be used on bottles of sensitive liquids such as milk, beer, cosmetics or medicines.

It will be apparent to persons skilled in the art that many modifications and variations may be made in relation to embodiments which have been particularly described herein; merely by way of' illustration only, an aluminum film or foil can be gradiently doped. Accordingly, the invention is not. to be construed as limited to such embodiments as have been particularly described, rather the concept, scope and spirit of the invention will be appreciated from the claims which follow.

14 SUBSTITUTE SHEET

Claims

1. Aluminum which comprises dopant in an amount effective to provide controlled oxidation of the aluminum in presence of oxygen and thereby to prevent formation of an oxidation-resistant aluminum oxide layer on the aluminum.

2. Aluminum according to claim 1, wherein said dopant comprises at least one metal selected from the group consisting of lithium, sodium, -potassium, rubidium, caesium, brlim magnesium, calcium, strontium and barium.

3. Aluminum in a form selected from foils and films, which comrises in at least an outer surface layer thereof, dopant in an amount effective to provide controlled damage of the aluminum suzf ace oxide layer which forms on exposure of the aluminum surface to air.

4. Aluminum according to claim 3, wherein said dopan't comprises at least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium.

A flexible laminar sheet material which comprises aluminum in a form selected from foils and fi):ms, as defined In claim 3, and having a polymeric layer on one side thereof.

6. A flexible laminar sheet. material according to claim wherein said polymeric layer is a breathable polymeric layer. SUBSTITUTE SHEET WO 93/09946 PCT/US92/09727

7. A flexible laminar sheet material which comprises aluminum in a form selected from foils and films, as defined in claim 3, and having a polymeric layer on each side thereof.

8. A flexible laminar sheet material according to claim 7, wherein the polymeric layer on at least one side of the doped aluminum foil is a breathable polymeric layer.

9. A flexible laminar sheet material which comprises aluminum in a form selected from foils and films, as defined in claim 4, and having a polymeric layer on one side thereof.

A flexible laminar sheet material according to claim 9. wherein said polymeric layer is a breathable polymeric layer.

11. A flexible laminar sheet material which' comprises aluminum in a form selected from foils and films, as defined in claim 4, and having a polymeric layer on each side thereof.

12. A flexible laminar sheet material according to claim 11, wherein the polymeric layer on at least one side. of the doped aluminum foil is a breathable polymeric layer.

13. A flexible laminar sheet material which comprises polymeric film having on one side thereof at least one layer of doped aluminum, wherein said doped aluminum has been doped with a dopant comprising at least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium. 16 SUBSTITUTE SHEET pCT/US92/09727 WO 93/09946

14. A flexible laminar sheet material according to claim 13, wherein said polymeric film has on one side thereof single layer of doped aluminum.

A flexible laminar sheet material according to claim 13, wherein said polymeric film has on one side thereof at least two layers of aluminum and at least the layer of aluminum remote from said polymeric film is a doped aluminum layer.

16. A flexible iaminar sheet material according to claim wherein said polymeric film has one one side thereof an undoped aluminum layer and superimposed on said undoped layer a doped aluminum layer.

17. A flexible laminar sheet material according to claim. 137 which comprises additionally a breathable polymeric layer superimposed on the at least one doped aluminum layer, said breathable polymeric layer being the outermost layer remote from said polymeric film. is.

A pacl-aged article of commerce which is characterized by at least one of the the following features and namely: at least part of the packaging comprises at least one material selected from doped aluminum foil and flexible laminar sheet material incorporating doped aluminnm; it contains internally, doped aluminum, said doped aluminum being aluminum doped with a dopant which comprises at least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium. 17 SUBSTITUTE SHEET I T- rr^era-----c -18-

19. An article according to claim 18 which comprises a product selected from cometstibles and drugs for human use, wherein said dopant is restricted to non-toxic dopant metals selected from said group.

Doped aluminium substantially as herein described with reference to the accompanying drawings.

21. A flexible laminar sheet material substantially as herein described with reference to the accompanying drawings.

22. A packaged article substantially as herein described with reference to the accompanying drawings. DATED this 28th day of November, 1994. SHIRAT ENTERPRISES LTD. and 20 LAWRENCE GOLDMUNTZ By their Patent Attorneys DAVIES COLLISON CAVE t Cttt St i r I