CA2142895C - Vaccum deposition and curing of liquid monomers - Google Patents
Vaccum deposition and curing of liquid monomers Download PDFInfo
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- CA2142895C CA2142895C CA002142895A CA2142895A CA2142895C CA 2142895 C CA2142895 C CA 2142895C CA 002142895 A CA002142895 A CA 002142895A CA 2142895 A CA2142895 A CA 2142895A CA 2142895 C CA2142895 C CA 2142895C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/067—Metallic effect
- B05D5/068—Metallic effect achieved by multilayers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0493—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases using vacuum
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- 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
The present invention is the formation of solid polymer layers under vacuum.
More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used is an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacu-um deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteris-tics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for cur-ing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.
More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used is an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacu-um deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteris-tics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for cur-ing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.
Description
W~ 94/0428 PCT/~.1593/072fl9 VACUUM DEPOSITION AND CURING OF LIQUID MONOMERS
.The present invention relates generally to a method of making multilayer laminate structures from polxmers and metals and/or oxide. More specifically, the present invention relates to farmihg solid polymer laminate 3.e layers under. vacuum. Additional la~r~rs of polymer or metal or oxide may be added under vacuum as well.
HA~GFtflUND OF TFiE INVENTION
La~ai~nate structures are used ' in many applications including but not limited to electronic devices, packag 35 ing Ana aerial , and solar ref lec tars . I.ar,~xnate s tzuc tares in'elec~ronic devices are found in devises including but not l~.mited t~ circuit elements and elecarochromic devices wherein conductive polymer layers are Eombined arad may include a metal ~.ayer and/or an oxide layer.
2Q ,Elactrochramic devices include but are not limited tc~' swi~chable ~arr~rs and switch~ble widows. Circuit elements include active elements, for example fuel cells and batter~:es, and passive' ele~eh~s, for ex~mpZe capacitors.
25 Presently; many laminate structures are made with solid polymer laminaite layers: In packaging material and s~lar reflectors, a petal layer may be added to enhance ~pta.cal reflectance. In electronic devices, a metal layer may be added to enhance electrical condueti.vit~r. .
3o In packaging material and solar reflectors, it is not necessary that the polymer layer or layers be conductive, whereas ~.n electronic devices, especially batteries, the W~ 9480425 2 ~ ~ ~ ~ ~ ~ PCTlIJS9~/07209 polymer layers must be conductive to act as electrolytes, anades, and cathodes. Certain polymers when doped with selected salts are known to make suitable solid polymer ion conductive layers. Polymers known to be useful include but are not limited to polyethyleneoxide, polypropyleneoxide, polyorgansulfides,,~~and polyanaline.
Suitable salts include but are not 1~~:~nited to lithium salts, for example lithium perchloxate, and lithium hexafluoxoarseriate. Although the anode, cathode, and 7lp , electrolyte layers :may all be of solid polymer material, when making a lith~.um polymer battery, it is preferred to have a layer of lithium metal as an anode.
Laminate structures further include electrochromic devices wherein an electrolyte is sandwiched between 15; eleetrochromic oxide layers. Conductive layers are placed ~n the electrochromic oxide layers for connection to an eleetri~al power source. Additional structural or protective la~ei~s may be added. to enclose an electr~-chromic assembly.
Other polymers having added compounds, ~.nc3~:di~g bud not li.a~ited to conductive powders and dyes, may be made by the present invention.
Presently, mass production of polymer and metal laminate structures used for electronic devices, and 2~ espeeially~ '~atter.ies, relies upon assembling preformed layers ~f polymer with a thin metal foil. Polymer layers are formed a.n . product~.on quantities by depositing a thin layer of a monomer onto a moving, substrate that carries the monomer layer while and until it 'is cured. Many 30 means for formingpolymer layers are available, including but not limited to physical or mechanical liquid-monomer spreading appaxati; for example, roll coat~rs, gravure .
roll coaters, wire wound rods, doctor blades, and slotted dies, as well as means for evaporation and deposition of 35 a monomer vapor, for example polymer multilayer deposi-tion. In any means having a moving substrate, the ... ... ~. ; .. , . , , .. .,. : : _ , ,. ;. , :;. _ : , .: ~ ;: -. ~ - .:: .
;.., _2~42~9~:
dV0 94/Q4285 PC'1"/US93/0°7209 . substrate has a velocity different from a nozzle or bath that deposits the liquid monomer onto the substrate.
Hence, the term "moving substrate" as used herein excludes a situation wherein there is no relative motion or velocity differential between substrate and liquid~-~aonomer, dispensing means.
the polymer multilayer deposition technique is distinct from liquid-monomer spreading techniques because polymer mult~;laye~ deposition requires flash evaporation of the monomer. First, a monomer ,is atomized into a heated chamber that is under vacuum. Within the heated chamber the monomer droplets are evaporated, then exit the heated chamber, and monomer vapor condenses upon a substrate and is subsequently cured.
Curing may be done by any means including but not limited to hear, infrared light, ultraviolet light, el~Ctron beam, ~r~d other radiation.
y~eh fabricating a battery, several techniques are used to combing a tt~.in metal layer with a conducive pnl~er layer. One techni~ae of battery fabrication is to' combine a metal foil with a conductive polymer layer by press laonding a metal foil layer to a solid conductive polymer layer. Another technique is to spread uncured conductive~~monomer onto a metal foil and subsequently cure the conductive monomer to form a solid conductive polymer layer. Use of metal foil, especially lithium metal f~il, results in minimum metal ~hicknesses of from about W.S mils (40 micrometers) to about 2 mils (5o micrometers):
' 30 Other battery fabrication techniques include ma3cing a thin metal layer by, sputtering, plating, or vacuum depositing metal onto a metal substrate. A conductive polymer is-then placed in contact with the metal: Hither solid conductive polymer or uncured conductive monomer may be brought into contact c~ith the metal to form the battery. Polymer laminate structures, including but not .Y .. .r.. . .' . ... . ,.:- ,:v;ww,:.: ~-:.,. ".,, , . , ,:, ,.":.,, ,..' , .
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a ,._ WO 94/04285 ~, ~ ~ ~ ~ ~ ~ PCT/US93/07209 limited to batteries, are made by a procedure wherein individual Dyers are sequentially and separately formed a then combined.
The perforynance and lifetime og..,~olymer/polymer and pol,ymer/metal laminate structures lend upon the quality of bonding between laminate layers: Bonding quality is affected by the presence of smal~.~;'' even microscale, areas of non-bonding at an interface between laminate layers.
The bonding ~.s~ especially critical between dissimilar layers; for example,, polymer and metal layers. In bat-teries, reduced bond quality between polymer and lithium metal Dyers results in greater ~.nternal resistance of.a battery produced with the laminate material and potential for "hot spots" upon recharging. In any structure, another problem with bonding dissimilar materials is chemical interaction between the materials. Areas of nc~n-boradinc~ ca~a enhance chemical interaction because they may contain non-inert species or provide different surface clxaracteristics at a boundary betwe°n banded anal 24 unbonded areas.
Bonding between layers is therefore of great impor-tance and i~ enhanced by several means, including but not limited to mechanical presses; and application of a second layer as a liquid with subsequent solidification up~n a first solid layer at atmospheric pressure. The ~fgicu.lty with these methods is that the law cost assembly of pressing or liquid application leads to low quality bonding as identified in ~1.S. Pat. No. 4,098,965, issued July 4, 1976, to Kinsman, column'1., lines 47-50, wherein he states "[g]aces usually air, [that] are .
included in the void regions of , the ~ battery dear ing assembly . . .":
Likewise, bonding between layers within electro chromic devices and other laminate structures is directly related to the performance of the devices.
It is of great interest to those skilled in the art, then, to make batteries and other laminate structures having high bond quality while making them in a cost effective manner.
SUMMARY OF THE INVENTION
The present invention is the formation of solid polymer layers under vacuum. More specifically, according to a first aspect of the present invention, "standard" polymer-layer making equipment that is generally used in an atmospheric environment is placed in a vacuum with an additional step of degassing the monomer material prior to injection into the vacuum.
Additionally, other layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers.
Advantages of forming polymer layers in a vacuum include use of less to no photoinitiator for curing, faster curing, and fewer impurities in the polymer. Further advantages are improvement in material properties, including no trapped gas, resulting in greater density and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.
One embodiment of the first aspect comprises (a) placing a moving substrate into a vacuum chamber; (b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber; (c) degassing a first liquid monomer; (d) depositing a first thin layer of the degassed liquid monomer from the liquid-monomer spreading apparatus onto the moving substrate within the vacuum chamber; and (i) curing the first thin layer.
- 5a -According to a second aspect of the invention, fabrication of laminate structures are carried out nearly simultaneously within a single vacuum chamber.
One embodiment of the second aspect is directed to a method of making a lithium polymer battery, comprising the steps of: (a) placing a moving substrate into a vacuum chamber; (b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber; (c) degassing a liquid monomer cathode material;
(d) depositing a thin layer of the liquid monomer cathode material onto the moving substrate; (e) curing the monomer cathode material forming a solid cathode polymer; and (f) depositing and curing a thin layer of monomer electrolyte material onto the cathode, forming a solid polymer electrolyte with subsequent deposition of lithium metal onto the electrolyte, forming an anode.
Another embodiment of the second aspect is directed to a method of making a lithium polymer battery, comprising the steps of: (a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber; (c) degassing a liquid monomer electrolyte material; (d) depositing a thin layer of lithium metal onto the moving substrate and forming an anode; (e) depositing a thin layer of degassed monomer electrolyte material onto the lithium metal; (f) curing the monomer electrolyte material forming a solid electrolyte polymer; and (g) depositing and curing a thin layer of monomer cathode material onto the electrolyte, forming a - 5b -solid polymer cathode.
Still another embodiment of the second aspect is directed to a method of making electrochromic devices comprising the steps of: (a) placing a moving substrate into a vacuum chamber; (b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber; (c) degassing a liquid monomer electrolyte material; (d) depositing a first conductive oxide layer onto the moving substrate; (e) depositing a first electrochromic oxide layer onto the first conductive layer; (f) depositing the liquid monomer electrolyte material onto the first electrochromic oxide layer; (g) curing the liquid monomer electrolyte to a solid polymer electrolyte; (h) depositing a second electrochromic oxide layer onto the solid polymer electrolyte, and (i) depositing a second conductive oxide layer onto the second electrochromic oxide layer.
A third aspect of the invention provides an apparatus for making a solid polymer layer, comprising: (a) a moving substrate; (b) means for creating a vacuum about the moving substrate; (c) means for degassing the liquid monomer; and (d) means for depositing a first thin layer of degassed liquid monomer onto the moving substrate followed by means for curing the liquid monomer and forming a first solid polymer layer.
The subject matter of the present invention is particularly pointed out and distinctly claimed in the concluding portion of this specification. However, both the organization - 5c -and method of operation, together with further advantages and objects thereof, may best be understood by reference to the following detailed description.
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'VVO 94/0425 ~ ~ ~ ~ ~ ~ ~ fCI'/LJS93/07209V~.
w DESCRIPTION OF THE PREFERRED EMHODIMENT(S) The method of the present invention is making a solid polymer ~.ayer by utili2ing two known steps irr combination with two additional ~st~eps that had not been l combined pxiar to the present in~'ention. The known steps of depositing ~ thin layer ,~,pf ligu~.d monomer onto a moving substrate fol2owed by~' cur~.ngsaid monomer and form.~.ng the sol id Polymer ~.ayer, are eomby.ned with tie steps of (a) placing the moving substrate into a vacuum 1p chamber, and (b) degassing the monomer prior to deposi-ting the degassed monomer onto the moving substrate in tha vacuum chamber.
The substrate may be a temporary substrate from which the solid polymer layer product is removed after 1.5 curing, or the substrate may ~e a permanent substrate forming park of the final product. The peraanent sub-stxate can be ae simple as a base polymer layer having a metala,aed u.rgacs, ~br example., a .sel.ar reflector. The presar~t invention may be used to place a protective coat-'20 ing upon the metallic surface. The permanent substrata may be as complex as a many-layered monolithic electronic device, fox example, a capacitor iri which the present inv~.ntion may b~ used to, place multiple po?ymer and petal layers o construct the device.
25 Accord~..ag to the presani invention, any polymer layer making method d~ne in air or other atmosphere ~a~r be adapted to be carried out in a;vacuum.
The apparatus of the present invention is a comlbi-nation of known means with additional means that had not 3p been combined prior to the present invention. apparatus for making a solid polymer layer includes a moving sub-strata together with means fox depositing a thin layer of liquid monomer onto the moving -substrate, followed by means for curing-the liquid monomer and forming the solid 35 p~lymer. These means are combined with (a) means for ,. _21~2~9~
VNCA 94/04285 ~~ ' PGT/U~93/07209 creating a vacuum about the moving substrate, and (b) means for degassing the liquid monomer prior to deposi-ting the degassed liqu~.d monomer onto the moving sub~
strata in the vacuum.
For making a polyzaer/metal laminate structure, 'the metal is vacuum deposited onto a cured solid polymer layer. ~ Alternatively, the metal may be vacuum deposited onto a substrate, then liquid monomer deposited and sDre3d uncle; vacuum onto the mQtal surface. Any vacuum ~;0 deposition technique may be used, but electron beam evaporation is preferred, especially far vacuum deposi~
Lion of lithium metal. While any metal thickness is achievable with vacuum deposition techniques, a practical range of thickness is from about 10 angstroms to about 0.4 m~.ls (1p micrometers). For making a lithium polymer battery, it is preferred that the cathode and electrolyte are conducive polymer layers and that the anode is lithium metal.
Fnr ~i.ng a..dd.itional p~alymer/ oxa.de. la~.in.at.e strut 2p ture, the oxide is vacuum deposited onto a cured solid polymer layer. Any oxide vacuum deposition technique may be used, but reactive sputtering is preferred to maintain composition of the oxide layer and improved control over Film structure.
Creating a vacuum about a moving substrate may be done in navy ways, including housing an entire solid polymer°~aking apparatus in a vacuum chamber. Alterna~
tively, a vacuum chamber may contain a moving substrate and a nozzle ~r coating head penetrating a wall of the 3p vacuum chamber f~r admitting liquid monomer material.
Degassing of the liquid monomer nay b~ carried out :in any way, but it is preferred that the monomer be degassed by stirring it in a sealed vessel and removing resadual gas with a vacuum pump. The vacuum pump draws a 35. vacuum of ~ pressure that removes a sufficient quantity of gas from the liquid monomer to permit smooth flow of ~1~2~95 ~o .~aioaz~9 - PGT/US93/07z09 g _ the liquid monomer through a nozzle into the vacuum chamber with reduced entrained gas expansion, thereby preventing intermittent nozzle discharge, or spitting.
~'he amount of entrained gas mustt~' also be sufficiently low S
;>
i 5 to result in an acceptable qu~avity polymer. Acceptable quality includes but is not limited to the final polymer being free of void spaces and exhibiting a smooth surface.
The vacuum chamber may ac'c't save...~~_1 1=paid'-:~.~ro~er and other material inlets for permitting multiple monomer/polymer layers, curing means, as well as metal and/or oxide vacuum deposition means. With a multiple inlet vacuum .chamber, laminate structures are made in one pass through the chamber. For example, a polymer layer ~.5 may be cured , then a second metallic or oxide layer dep~s~,ted, and a subsequent polymer layer covering the second surface put in place, all within the vacuum chamber. Multiple passes of a product through the vacuum chamber.can d~vsof la~~re~ ~~.
By glacing liquid monomer spreading and vapor clap~sition of metal and/or oxide layer in the same vacuum chamber, the substrate velocity may be adjusted to accom-modate both processes. Additionally, the f lo~a of mate-ri.al through a nozzle may be adjusted to accc~odate both 25 rocesses. Similarl vacuum ressure is set low enough p y~ p try permit metal and/or oa~ide deposition.
A lithi:uz~ p~lymer battery requires a minimum of three layers, anode (lithium metal.) electrolyte polymer, and cathode polymer, respectively. Additional layers 3p include a cathode current collector metal layer, and an anode current collector metal layero The metal layers can be of any metal or metal alloy but are preferably metals or alloys that are chemically compatible and highly electrically conductive, for example gold, silver u35 and copper. M~reover, first and second polymer ~.nsulating layers may be deposited onto the currant :.l _ 2.~4~~~~ .
W~ 94101285 . PGT/US93/072Q~
g collectors to form a cell. Cells may be stacked with or without intervening polymer insulating material.
Thus, a method of making a lithium polymer battery, . according to the present invention has a minimum of siac 'steps. The.f first .three steps are equipment arrangement steps of (a) planing a moving substrate into a vacuum chamber, (b) placing a mechanical liquid-monomer spread-ing apparatus into the vacuum chamber, and (c) degassing a liquid monomer eatta.ode mate...rial. ?'he next three steps ZO are material deposition steps of (d)depositing a thin layer of the liquid monomer cathode material onto the mowing substrate, (e) curing the monomer cathode material and forming a solid cathode polymer, and (f) depositing and curing a thin layer of monomer electrolyte material onto said cath~de, forming a solid polymer electrolyte with subsequen'~ deposition of lithium metal onto said electrolyte, forming an anode.
For particular applications requiring current _ c~actcrs and protective insulating layer, two steps ~0 mad precede the material deposition steps. Specifically, the additional steps of (g) depositing a first monomer insulating material layer onto the moving substrate and curing the first mon~mer insulating material layer in advance of step (d;) deposition of monomer cathode, and ~5 ~~) depositing a cathode current collector metal onto the cured insulating material in advance of step (d) depo-sition of monomer cathode. Additionally, two steps may follow the material deposition steps, vis the steps of (i) depositing an anode current collector onto the anode, ~p and (j) depositing a second monr~mer insulating layer onto the anode current collector. and curing the second monomer insulating layer:
~leatrochromic devices are similar to lithium polymer batteries in the aspect of an electrolyte layer 35 combined with conductive layers. I~owever, the specific layers are distinct ~o that the method of making "' ; " .
. :.
'~O 9A1~4285 . F(."I"1U~93/07209 214~'~95 ~ .
- - io -electrochromic devices according to the present invention has the same equipment arrangement steps of (a) placing a moving substrate into a vacuum chamber, (b) placing a mechanical liquid-moncimer spread'i~g apparatus into the vacuum chamber, and (c) degas~~~ing a liquid monomer .:, electrolyte material. However,' the material deposition steps are (d) depositing a first conductive oxide layer onto the moving substrate, (e) depositing a first electrochromic , oxide layer onto the f ~ gist ccnd~active 1p axide l,ay~er, (f) depositing the liquid monomer electro-lyte mzaterial onto the first electrochromic oxide layer, (g) curing the liquid monomer electrolyte to a solid polymer electrolyte, (hj depositing a second electro-chromic oxide layer onto the solid polymer electrolyte, ~5 and (i) depositing a second conductive oxide layer onto the second electrochromic oxide layer.
~y cd~ductive oxide layer matera.a~. may be used, but preferred conductive oxide materials include, for example indi~a~nn.. oxide, i ndi urn-tin ox~.d~, tin o~.de, and 2~ zinc oxide: Indium oxides are preferred. ~,Zectrochromic oxide materials include but are not limited to tungsten o~eides, iridium oxides, and vanadium oxides.
y~ile a preferred embodiment of the present inven tion has been shown and described, it wild. be apparent to I 2~ those skilled in the art that many changes and modifica tions may be made without depaxvting froaa the invention in its broader aspects: The appended claims are therefore intended o cover all, such changes and modifications as fall within the true spirit and scope of the invention.
.The present invention relates generally to a method of making multilayer laminate structures from polxmers and metals and/or oxide. More specifically, the present invention relates to farmihg solid polymer laminate 3.e layers under. vacuum. Additional la~r~rs of polymer or metal or oxide may be added under vacuum as well.
HA~GFtflUND OF TFiE INVENTION
La~ai~nate structures are used ' in many applications including but not limited to electronic devices, packag 35 ing Ana aerial , and solar ref lec tars . I.ar,~xnate s tzuc tares in'elec~ronic devices are found in devises including but not l~.mited t~ circuit elements and elecarochromic devices wherein conductive polymer layers are Eombined arad may include a metal ~.ayer and/or an oxide layer.
2Q ,Elactrochramic devices include but are not limited tc~' swi~chable ~arr~rs and switch~ble widows. Circuit elements include active elements, for example fuel cells and batter~:es, and passive' ele~eh~s, for ex~mpZe capacitors.
25 Presently; many laminate structures are made with solid polymer laminaite layers: In packaging material and s~lar reflectors, a petal layer may be added to enhance ~pta.cal reflectance. In electronic devices, a metal layer may be added to enhance electrical condueti.vit~r. .
3o In packaging material and solar reflectors, it is not necessary that the polymer layer or layers be conductive, whereas ~.n electronic devices, especially batteries, the W~ 9480425 2 ~ ~ ~ ~ ~ ~ PCTlIJS9~/07209 polymer layers must be conductive to act as electrolytes, anades, and cathodes. Certain polymers when doped with selected salts are known to make suitable solid polymer ion conductive layers. Polymers known to be useful include but are not limited to polyethyleneoxide, polypropyleneoxide, polyorgansulfides,,~~and polyanaline.
Suitable salts include but are not 1~~:~nited to lithium salts, for example lithium perchloxate, and lithium hexafluoxoarseriate. Although the anode, cathode, and 7lp , electrolyte layers :may all be of solid polymer material, when making a lith~.um polymer battery, it is preferred to have a layer of lithium metal as an anode.
Laminate structures further include electrochromic devices wherein an electrolyte is sandwiched between 15; eleetrochromic oxide layers. Conductive layers are placed ~n the electrochromic oxide layers for connection to an eleetri~al power source. Additional structural or protective la~ei~s may be added. to enclose an electr~-chromic assembly.
Other polymers having added compounds, ~.nc3~:di~g bud not li.a~ited to conductive powders and dyes, may be made by the present invention.
Presently, mass production of polymer and metal laminate structures used for electronic devices, and 2~ espeeially~ '~atter.ies, relies upon assembling preformed layers ~f polymer with a thin metal foil. Polymer layers are formed a.n . product~.on quantities by depositing a thin layer of a monomer onto a moving, substrate that carries the monomer layer while and until it 'is cured. Many 30 means for formingpolymer layers are available, including but not limited to physical or mechanical liquid-monomer spreading appaxati; for example, roll coat~rs, gravure .
roll coaters, wire wound rods, doctor blades, and slotted dies, as well as means for evaporation and deposition of 35 a monomer vapor, for example polymer multilayer deposi-tion. In any means having a moving substrate, the ... ... ~. ; .. , . , , .. .,. : : _ , ,. ;. , :;. _ : , .: ~ ;: -. ~ - .:: .
;.., _2~42~9~:
dV0 94/Q4285 PC'1"/US93/0°7209 . substrate has a velocity different from a nozzle or bath that deposits the liquid monomer onto the substrate.
Hence, the term "moving substrate" as used herein excludes a situation wherein there is no relative motion or velocity differential between substrate and liquid~-~aonomer, dispensing means.
the polymer multilayer deposition technique is distinct from liquid-monomer spreading techniques because polymer mult~;laye~ deposition requires flash evaporation of the monomer. First, a monomer ,is atomized into a heated chamber that is under vacuum. Within the heated chamber the monomer droplets are evaporated, then exit the heated chamber, and monomer vapor condenses upon a substrate and is subsequently cured.
Curing may be done by any means including but not limited to hear, infrared light, ultraviolet light, el~Ctron beam, ~r~d other radiation.
y~eh fabricating a battery, several techniques are used to combing a tt~.in metal layer with a conducive pnl~er layer. One techni~ae of battery fabrication is to' combine a metal foil with a conductive polymer layer by press laonding a metal foil layer to a solid conductive polymer layer. Another technique is to spread uncured conductive~~monomer onto a metal foil and subsequently cure the conductive monomer to form a solid conductive polymer layer. Use of metal foil, especially lithium metal f~il, results in minimum metal ~hicknesses of from about W.S mils (40 micrometers) to about 2 mils (5o micrometers):
' 30 Other battery fabrication techniques include ma3cing a thin metal layer by, sputtering, plating, or vacuum depositing metal onto a metal substrate. A conductive polymer is-then placed in contact with the metal: Hither solid conductive polymer or uncured conductive monomer may be brought into contact c~ith the metal to form the battery. Polymer laminate structures, including but not .Y .. .r.. . .' . ... . ,.:- ,:v;ww,:.: ~-:.,. ".,, , . , ,:, ,.":.,, ,..' , .
.:
-r.. ~:...' ..., .",~;-, ..,..-... . ::,-... . .... ..... .,, . . :~:. . .
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a ,._ WO 94/04285 ~, ~ ~ ~ ~ ~ ~ PCT/US93/07209 limited to batteries, are made by a procedure wherein individual Dyers are sequentially and separately formed a then combined.
The perforynance and lifetime og..,~olymer/polymer and pol,ymer/metal laminate structures lend upon the quality of bonding between laminate layers: Bonding quality is affected by the presence of smal~.~;'' even microscale, areas of non-bonding at an interface between laminate layers.
The bonding ~.s~ especially critical between dissimilar layers; for example,, polymer and metal layers. In bat-teries, reduced bond quality between polymer and lithium metal Dyers results in greater ~.nternal resistance of.a battery produced with the laminate material and potential for "hot spots" upon recharging. In any structure, another problem with bonding dissimilar materials is chemical interaction between the materials. Areas of nc~n-boradinc~ ca~a enhance chemical interaction because they may contain non-inert species or provide different surface clxaracteristics at a boundary betwe°n banded anal 24 unbonded areas.
Bonding between layers is therefore of great impor-tance and i~ enhanced by several means, including but not limited to mechanical presses; and application of a second layer as a liquid with subsequent solidification up~n a first solid layer at atmospheric pressure. The ~fgicu.lty with these methods is that the law cost assembly of pressing or liquid application leads to low quality bonding as identified in ~1.S. Pat. No. 4,098,965, issued July 4, 1976, to Kinsman, column'1., lines 47-50, wherein he states "[g]aces usually air, [that] are .
included in the void regions of , the ~ battery dear ing assembly . . .":
Likewise, bonding between layers within electro chromic devices and other laminate structures is directly related to the performance of the devices.
It is of great interest to those skilled in the art, then, to make batteries and other laminate structures having high bond quality while making them in a cost effective manner.
SUMMARY OF THE INVENTION
The present invention is the formation of solid polymer layers under vacuum. More specifically, according to a first aspect of the present invention, "standard" polymer-layer making equipment that is generally used in an atmospheric environment is placed in a vacuum with an additional step of degassing the monomer material prior to injection into the vacuum.
Additionally, other layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers.
Advantages of forming polymer layers in a vacuum include use of less to no photoinitiator for curing, faster curing, and fewer impurities in the polymer. Further advantages are improvement in material properties, including no trapped gas, resulting in greater density and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.
One embodiment of the first aspect comprises (a) placing a moving substrate into a vacuum chamber; (b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber; (c) degassing a first liquid monomer; (d) depositing a first thin layer of the degassed liquid monomer from the liquid-monomer spreading apparatus onto the moving substrate within the vacuum chamber; and (i) curing the first thin layer.
- 5a -According to a second aspect of the invention, fabrication of laminate structures are carried out nearly simultaneously within a single vacuum chamber.
One embodiment of the second aspect is directed to a method of making a lithium polymer battery, comprising the steps of: (a) placing a moving substrate into a vacuum chamber; (b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber; (c) degassing a liquid monomer cathode material;
(d) depositing a thin layer of the liquid monomer cathode material onto the moving substrate; (e) curing the monomer cathode material forming a solid cathode polymer; and (f) depositing and curing a thin layer of monomer electrolyte material onto the cathode, forming a solid polymer electrolyte with subsequent deposition of lithium metal onto the electrolyte, forming an anode.
Another embodiment of the second aspect is directed to a method of making a lithium polymer battery, comprising the steps of: (a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber; (c) degassing a liquid monomer electrolyte material; (d) depositing a thin layer of lithium metal onto the moving substrate and forming an anode; (e) depositing a thin layer of degassed monomer electrolyte material onto the lithium metal; (f) curing the monomer electrolyte material forming a solid electrolyte polymer; and (g) depositing and curing a thin layer of monomer cathode material onto the electrolyte, forming a - 5b -solid polymer cathode.
Still another embodiment of the second aspect is directed to a method of making electrochromic devices comprising the steps of: (a) placing a moving substrate into a vacuum chamber; (b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber; (c) degassing a liquid monomer electrolyte material; (d) depositing a first conductive oxide layer onto the moving substrate; (e) depositing a first electrochromic oxide layer onto the first conductive layer; (f) depositing the liquid monomer electrolyte material onto the first electrochromic oxide layer; (g) curing the liquid monomer electrolyte to a solid polymer electrolyte; (h) depositing a second electrochromic oxide layer onto the solid polymer electrolyte, and (i) depositing a second conductive oxide layer onto the second electrochromic oxide layer.
A third aspect of the invention provides an apparatus for making a solid polymer layer, comprising: (a) a moving substrate; (b) means for creating a vacuum about the moving substrate; (c) means for degassing the liquid monomer; and (d) means for depositing a first thin layer of degassed liquid monomer onto the moving substrate followed by means for curing the liquid monomer and forming a first solid polymer layer.
The subject matter of the present invention is particularly pointed out and distinctly claimed in the concluding portion of this specification. However, both the organization - 5c -and method of operation, together with further advantages and objects thereof, may best be understood by reference to the following detailed description.
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'VVO 94/0425 ~ ~ ~ ~ ~ ~ ~ fCI'/LJS93/07209V~.
w DESCRIPTION OF THE PREFERRED EMHODIMENT(S) The method of the present invention is making a solid polymer ~.ayer by utili2ing two known steps irr combination with two additional ~st~eps that had not been l combined pxiar to the present in~'ention. The known steps of depositing ~ thin layer ,~,pf ligu~.d monomer onto a moving substrate fol2owed by~' cur~.ngsaid monomer and form.~.ng the sol id Polymer ~.ayer, are eomby.ned with tie steps of (a) placing the moving substrate into a vacuum 1p chamber, and (b) degassing the monomer prior to deposi-ting the degassed monomer onto the moving substrate in tha vacuum chamber.
The substrate may be a temporary substrate from which the solid polymer layer product is removed after 1.5 curing, or the substrate may ~e a permanent substrate forming park of the final product. The peraanent sub-stxate can be ae simple as a base polymer layer having a metala,aed u.rgacs, ~br example., a .sel.ar reflector. The presar~t invention may be used to place a protective coat-'20 ing upon the metallic surface. The permanent substrata may be as complex as a many-layered monolithic electronic device, fox example, a capacitor iri which the present inv~.ntion may b~ used to, place multiple po?ymer and petal layers o construct the device.
25 Accord~..ag to the presani invention, any polymer layer making method d~ne in air or other atmosphere ~a~r be adapted to be carried out in a;vacuum.
The apparatus of the present invention is a comlbi-nation of known means with additional means that had not 3p been combined prior to the present invention. apparatus for making a solid polymer layer includes a moving sub-strata together with means fox depositing a thin layer of liquid monomer onto the moving -substrate, followed by means for curing-the liquid monomer and forming the solid 35 p~lymer. These means are combined with (a) means for ,. _21~2~9~
VNCA 94/04285 ~~ ' PGT/U~93/07209 creating a vacuum about the moving substrate, and (b) means for degassing the liquid monomer prior to deposi-ting the degassed liqu~.d monomer onto the moving sub~
strata in the vacuum.
For making a polyzaer/metal laminate structure, 'the metal is vacuum deposited onto a cured solid polymer layer. ~ Alternatively, the metal may be vacuum deposited onto a substrate, then liquid monomer deposited and sDre3d uncle; vacuum onto the mQtal surface. Any vacuum ~;0 deposition technique may be used, but electron beam evaporation is preferred, especially far vacuum deposi~
Lion of lithium metal. While any metal thickness is achievable with vacuum deposition techniques, a practical range of thickness is from about 10 angstroms to about 0.4 m~.ls (1p micrometers). For making a lithium polymer battery, it is preferred that the cathode and electrolyte are conducive polymer layers and that the anode is lithium metal.
Fnr ~i.ng a..dd.itional p~alymer/ oxa.de. la~.in.at.e strut 2p ture, the oxide is vacuum deposited onto a cured solid polymer layer. Any oxide vacuum deposition technique may be used, but reactive sputtering is preferred to maintain composition of the oxide layer and improved control over Film structure.
Creating a vacuum about a moving substrate may be done in navy ways, including housing an entire solid polymer°~aking apparatus in a vacuum chamber. Alterna~
tively, a vacuum chamber may contain a moving substrate and a nozzle ~r coating head penetrating a wall of the 3p vacuum chamber f~r admitting liquid monomer material.
Degassing of the liquid monomer nay b~ carried out :in any way, but it is preferred that the monomer be degassed by stirring it in a sealed vessel and removing resadual gas with a vacuum pump. The vacuum pump draws a 35. vacuum of ~ pressure that removes a sufficient quantity of gas from the liquid monomer to permit smooth flow of ~1~2~95 ~o .~aioaz~9 - PGT/US93/07z09 g _ the liquid monomer through a nozzle into the vacuum chamber with reduced entrained gas expansion, thereby preventing intermittent nozzle discharge, or spitting.
~'he amount of entrained gas mustt~' also be sufficiently low S
;>
i 5 to result in an acceptable qu~avity polymer. Acceptable quality includes but is not limited to the final polymer being free of void spaces and exhibiting a smooth surface.
The vacuum chamber may ac'c't save...~~_1 1=paid'-:~.~ro~er and other material inlets for permitting multiple monomer/polymer layers, curing means, as well as metal and/or oxide vacuum deposition means. With a multiple inlet vacuum .chamber, laminate structures are made in one pass through the chamber. For example, a polymer layer ~.5 may be cured , then a second metallic or oxide layer dep~s~,ted, and a subsequent polymer layer covering the second surface put in place, all within the vacuum chamber. Multiple passes of a product through the vacuum chamber.can d~vsof la~~re~ ~~.
By glacing liquid monomer spreading and vapor clap~sition of metal and/or oxide layer in the same vacuum chamber, the substrate velocity may be adjusted to accom-modate both processes. Additionally, the f lo~a of mate-ri.al through a nozzle may be adjusted to accc~odate both 25 rocesses. Similarl vacuum ressure is set low enough p y~ p try permit metal and/or oa~ide deposition.
A lithi:uz~ p~lymer battery requires a minimum of three layers, anode (lithium metal.) electrolyte polymer, and cathode polymer, respectively. Additional layers 3p include a cathode current collector metal layer, and an anode current collector metal layero The metal layers can be of any metal or metal alloy but are preferably metals or alloys that are chemically compatible and highly electrically conductive, for example gold, silver u35 and copper. M~reover, first and second polymer ~.nsulating layers may be deposited onto the currant :.l _ 2.~4~~~~ .
W~ 94101285 . PGT/US93/072Q~
g collectors to form a cell. Cells may be stacked with or without intervening polymer insulating material.
Thus, a method of making a lithium polymer battery, . according to the present invention has a minimum of siac 'steps. The.f first .three steps are equipment arrangement steps of (a) planing a moving substrate into a vacuum chamber, (b) placing a mechanical liquid-monomer spread-ing apparatus into the vacuum chamber, and (c) degassing a liquid monomer eatta.ode mate...rial. ?'he next three steps ZO are material deposition steps of (d)depositing a thin layer of the liquid monomer cathode material onto the mowing substrate, (e) curing the monomer cathode material and forming a solid cathode polymer, and (f) depositing and curing a thin layer of monomer electrolyte material onto said cath~de, forming a solid polymer electrolyte with subsequen'~ deposition of lithium metal onto said electrolyte, forming an anode.
For particular applications requiring current _ c~actcrs and protective insulating layer, two steps ~0 mad precede the material deposition steps. Specifically, the additional steps of (g) depositing a first monomer insulating material layer onto the moving substrate and curing the first mon~mer insulating material layer in advance of step (d;) deposition of monomer cathode, and ~5 ~~) depositing a cathode current collector metal onto the cured insulating material in advance of step (d) depo-sition of monomer cathode. Additionally, two steps may follow the material deposition steps, vis the steps of (i) depositing an anode current collector onto the anode, ~p and (j) depositing a second monr~mer insulating layer onto the anode current collector. and curing the second monomer insulating layer:
~leatrochromic devices are similar to lithium polymer batteries in the aspect of an electrolyte layer 35 combined with conductive layers. I~owever, the specific layers are distinct ~o that the method of making "' ; " .
. :.
'~O 9A1~4285 . F(."I"1U~93/07209 214~'~95 ~ .
- - io -electrochromic devices according to the present invention has the same equipment arrangement steps of (a) placing a moving substrate into a vacuum chamber, (b) placing a mechanical liquid-moncimer spread'i~g apparatus into the vacuum chamber, and (c) degas~~~ing a liquid monomer .:, electrolyte material. However,' the material deposition steps are (d) depositing a first conductive oxide layer onto the moving substrate, (e) depositing a first electrochromic , oxide layer onto the f ~ gist ccnd~active 1p axide l,ay~er, (f) depositing the liquid monomer electro-lyte mzaterial onto the first electrochromic oxide layer, (g) curing the liquid monomer electrolyte to a solid polymer electrolyte, (hj depositing a second electro-chromic oxide layer onto the solid polymer electrolyte, ~5 and (i) depositing a second conductive oxide layer onto the second electrochromic oxide layer.
~y cd~ductive oxide layer matera.a~. may be used, but preferred conductive oxide materials include, for example indi~a~nn.. oxide, i ndi urn-tin ox~.d~, tin o~.de, and 2~ zinc oxide: Indium oxides are preferred. ~,Zectrochromic oxide materials include but are not limited to tungsten o~eides, iridium oxides, and vanadium oxides.
y~ile a preferred embodiment of the present inven tion has been shown and described, it wild. be apparent to I 2~ those skilled in the art that many changes and modifica tions may be made without depaxvting froaa the invention in its broader aspects: The appended claims are therefore intended o cover all, such changes and modifications as fall within the true spirit and scope of the invention.
Claims (13)
1. A method of making a solid polymer layer, comprising the steps of:
(a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber;
(c) degassing a liquid monomer;
(d) depositing a thin layer of the degassed liquid monomer from the liquid-monomer spreading apparatus onto the moving substrate within the vacuum chamber; and (i) curing the thin layer to form the solid polymer layer.
(a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber;
(c) degassing a liquid monomer;
(d) depositing a thin layer of the degassed liquid monomer from the liquid-monomer spreading apparatus onto the moving substrate within the vacuum chamber; and (i) curing the thin layer to form the solid polymer layer.
2. A method as recited in claim 1, further comprising the step of:
(e) vacuum depositing a metal or a conductive or electrochromic oxide onto the solid polymer layer.
(e) vacuum depositing a metal or a conductive or electrochromic oxide onto the solid polymer layer.
3. A method of making a lithium polymer battery, comprising the steps of:
(a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber;
(c) degassing a liquid monomer cathode material;
(d) depositing a thin layer of the liquid monomer cathode material onto the moving substrate;
(e) curing the monomer cathode material forming a solid cathode polymer; and (f) depositing and curing a thin layer of monomer electrolyte material onto the cathode, forming a solid polymer electrolyte with subsequent deposition of lithium metal onto the electrolyte, forming an anode.
(a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber;
(c) degassing a liquid monomer cathode material;
(d) depositing a thin layer of the liquid monomer cathode material onto the moving substrate;
(e) curing the monomer cathode material forming a solid cathode polymer; and (f) depositing and curing a thin layer of monomer electrolyte material onto the cathode, forming a solid polymer electrolyte with subsequent deposition of lithium metal onto the electrolyte, forming an anode.
4. The method as recited in claim 3, further comprising the steps of:
(g) depositing a monomer insulating material layer onto the moving substrate and curing the monomer insulating material layer in advance of step (d) deposition of the monomer cathode; and (h) depositing a cathode current collector metal onto the cured insulating material in advance of step (d) deposition of the monomer cathode.
(g) depositing a monomer insulating material layer onto the moving substrate and curing the monomer insulating material layer in advance of step (d) deposition of the monomer cathode; and (h) depositing a cathode current collector metal onto the cured insulating material in advance of step (d) deposition of the monomer cathode.
5. The method as recited in claim 4, further comprising the steps of:
(i) depositing an anode current collector onto the anode; and (j) depositing a further monomer insulating layer onto the anode current collector and curing the further monomer insulating layer.
(i) depositing an anode current collector onto the anode; and (j) depositing a further monomer insulating layer onto the anode current collector and curing the further monomer insulating layer.
6. A method of making a lithium polymer battery, comprising the steps of:
(a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber;
(c) degassing a liquid monomer electrolyte material;
(d) depositing a thin layer of lithium metal onto the moving substrate and forming an anode;
(e) depositing a thin layer of degassed monomer electrolyte material onto the lithium metal;
(f) curing the monomer electrolyte material forming a solid electrolyte polymer; and (g) depositing and curing a thin layer of monomer cathode material onto the electrolyte, forming a solid polymer cathode.
(a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber;
(c) degassing a liquid monomer electrolyte material;
(d) depositing a thin layer of lithium metal onto the moving substrate and forming an anode;
(e) depositing a thin layer of degassed monomer electrolyte material onto the lithium metal;
(f) curing the monomer electrolyte material forming a solid electrolyte polymer; and (g) depositing and curing a thin layer of monomer cathode material onto the electrolyte, forming a solid polymer cathode.
7. The method as recited in claim 6, further comprising the steps of:
(h) depositing a monomer insulating material layer onto the moving substrate and curing the first monomer insulating material layer in advance of step (d) deposition of lithium metal; and (i) depositing an anode current collector metal onto the cured insulating material in advance of step (d) deposition of lithium metal.
(h) depositing a monomer insulating material layer onto the moving substrate and curing the first monomer insulating material layer in advance of step (d) deposition of lithium metal; and (i) depositing an anode current collector metal onto the cured insulating material in advance of step (d) deposition of lithium metal.
8. The method as recited in claim 7, further comprising the steps of:
(j) depositing a cathode current collector onto the cathode; and (k) depositing a further monomer insulating layer onto the cathode current collector and curing the further monomer insulating layer.
(j) depositing a cathode current collector onto the cathode; and (k) depositing a further monomer insulating layer onto the cathode current collector and curing the further monomer insulating layer.
9. A method of making electrochromic devices comprising the steps of:
(a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber;
(c) degassing a liquid monomer electrolyte material;
(d) depositing a first conductive oxide layer onto the moving substrate;
(e) depositing a first electrochromic oxide layer onto the first conductive oxide layer;
(f) depositing the liquid monomer electrolyte material onto the first electrochromic oxide layer;
(g) curing the liquid monomer electrolyte to a solid polymer electrolyte;
(h) depositing a second electrochromic oxide layer onto the solid polymer electrolyte; and (i) depositing a second conductive oxide layer onto the second electrochromic oxide layer.
(a) placing a moving substrate into a vacuum chamber;
(b) placing a mechanical liquid-monomer spreading apparatus into the vacuum chamber;
(c) degassing a liquid monomer electrolyte material;
(d) depositing a first conductive oxide layer onto the moving substrate;
(e) depositing a first electrochromic oxide layer onto the first conductive oxide layer;
(f) depositing the liquid monomer electrolyte material onto the first electrochromic oxide layer;
(g) curing the liquid monomer electrolyte to a solid polymer electrolyte;
(h) depositing a second electrochromic oxide layer onto the solid polymer electrolyte; and (i) depositing a second conductive oxide layer onto the second electrochromic oxide layer.
10. An apparatus for making a solid polymer layer, comprising:
(a) a moving substrate;
(b) means for creating a vacuum about the moving substrate;
(c) means for degassing a liquid monomer; and (d) means for depositing a thin layer of a degassed liquid monomer onto the moving substrate followed by means for curing the liquid monomer and forming a solid polymer layer.
(a) a moving substrate;
(b) means for creating a vacuum about the moving substrate;
(c) means for degassing a liquid monomer; and (d) means for depositing a thin layer of a degassed liquid monomer onto the moving substrate followed by means for curing the liquid monomer and forming a solid polymer layer.
11. The apparatus as recited in claim 10, further comprising:
(e) additional means for vacuum depositing metal, means for depositing oxide, or means for depositing further layers of degassed liquid monomer together with means for curing the degassed liquid monomer.
(e) additional means for vacuum depositing metal, means for depositing oxide, or means for depositing further layers of degassed liquid monomer together with means for curing the degassed liquid monomer.
12. The apparatus as recited in claim 10, wherein the means for depositing is a mechanical liquid monomer spreading apparatus.
13. The apparatus as recited in claim 12, wherein the mechanical liquid monomer spreading apparatus is selected from the group consisting of roll coaters, wire wound rods, doctor blade coaters, and slotted die coaters.
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US07/933,447 | 1992-08-21 | ||
PCT/US1993/007209 WO1994004285A1 (en) | 1992-08-21 | 1993-07-30 | Vacuum deposition and curing of liquid monomers |
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CA2142895A1 CA2142895A1 (en) | 1994-03-03 |
CA2142895C true CA2142895C (en) | 2002-06-18 |
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Families Citing this family (142)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6524698B1 (en) | 1990-09-27 | 2003-02-25 | Helmuth Schmoock | Fluid impermeable foil |
JP2841923B2 (en) * | 1991-06-07 | 1998-12-24 | 日本製紙株式会社 | Manufacturing method of coated paper for printing |
US5260095A (en) * | 1992-08-21 | 1993-11-09 | Battelle Memorial Institute | Vacuum deposition and curing of liquid monomers |
US20040241454A1 (en) * | 1993-10-04 | 2004-12-02 | Shaw David G. | Barrier sheet and method of making same |
US5554470A (en) * | 1994-12-09 | 1996-09-10 | Xerox Corporation | Process and apparatus for manufacturing migration imaging members |
US5576129A (en) * | 1994-12-09 | 1996-11-19 | Xerox Corporation | Migration imaging members |
US5567544A (en) * | 1995-05-26 | 1996-10-22 | Boundless Corp. | Battery |
US5681615A (en) * | 1995-07-27 | 1997-10-28 | Battelle Memorial Institute | Vacuum flash evaporated polymer composites |
CH692135A5 (en) * | 1997-08-20 | 2002-02-28 | Tradition Establishment | A process for the metalizing coating of artifacts. |
US6224948B1 (en) | 1997-09-29 | 2001-05-01 | Battelle Memorial Institute | Plasma enhanced chemical deposition with low vapor pressure compounds |
US5902641A (en) * | 1997-09-29 | 1999-05-11 | Battelle Memorial Institute | Flash evaporation of liquid monomer particle mixture |
AU729498B2 (en) | 1998-03-23 | 2001-02-01 | Presstek, Inc. | Lithographic imaging with constructions having mixed organic/inorganic layers |
US6251334B1 (en) | 1998-03-23 | 2001-06-26 | Presstek, Inc. | Composite constructions having mixed organic/inorganic layers |
US6146225A (en) * | 1998-07-30 | 2000-11-14 | Agilent Technologies, Inc. | Transparent, flexible permeability barrier for organic electroluminescent devices |
US6398999B1 (en) | 1998-10-23 | 2002-06-04 | Avery Dennison Corporation | Process for making high aspect ratio reflective metal flakes |
US6863851B2 (en) * | 1998-10-23 | 2005-03-08 | Avery Dennison Corporation | Process for making angstrom scale and high aspect functional platelets |
US20030178734A1 (en) * | 1998-10-23 | 2003-09-25 | Karl Josephy | Process for making angstrom scale and high aspect functional platelets |
AU1339700A (en) | 1998-11-02 | 2000-05-22 | Presstek, Inc. | Transparent conductive oxides for plastic flat panel displays |
US6228434B1 (en) * | 1998-12-16 | 2001-05-08 | Battelle Memorial Institute | Method of making a conformal coating of a microtextured surface |
US6228436B1 (en) | 1998-12-16 | 2001-05-08 | Battelle Memorial Institute | Method of making light emitting polymer composite material |
US6207239B1 (en) | 1998-12-16 | 2001-03-27 | Battelle Memorial Institute | Plasma enhanced chemical deposition of conjugated polymer |
US6207238B1 (en) * | 1998-12-16 | 2001-03-27 | Battelle Memorial Institute | Plasma enhanced chemical deposition for high and/or low index of refraction polymers |
US6274204B1 (en) | 1998-12-16 | 2001-08-14 | Battelle Memorial Institute | Method of making non-linear optical polymer |
EP1145338B1 (en) | 1998-12-16 | 2012-12-05 | Samsung Display Co., Ltd. | Environmental barrier material for organic light emitting device and method of making |
US6217947B1 (en) | 1998-12-16 | 2001-04-17 | Battelle Memorial Institute | Plasma enhanced polymer deposition onto fixtures |
US6268695B1 (en) | 1998-12-16 | 2001-07-31 | Battelle Memorial Institute | Environmental barrier material for organic light emitting device and method of making |
US6110588A (en) | 1999-02-05 | 2000-08-29 | 3M Innovative Properties Company | Microfibers and method of making |
US6630231B2 (en) | 1999-02-05 | 2003-10-07 | 3M Innovative Properties Company | Composite articles reinforced with highly oriented microfibers |
US6503564B1 (en) * | 1999-02-26 | 2003-01-07 | 3M Innovative Properties Company | Method of coating microstructured substrates with polymeric layer(s), allowing preservation of surface feature profile |
US6172810B1 (en) | 1999-02-26 | 2001-01-09 | 3M Innovative Properties Company | Retroreflective articles having polymer multilayer reflective coatings |
US6358570B1 (en) | 1999-03-31 | 2002-03-19 | Battelle Memorial Institute | Vacuum deposition and curing of oligomers and resins |
US6506461B2 (en) * | 1999-03-31 | 2003-01-14 | Battelle Memorial Institute | Methods for making polyurethanes as thin films |
US6866901B2 (en) | 1999-10-25 | 2005-03-15 | Vitex Systems, Inc. | Method for edge sealing barrier films |
US6623861B2 (en) | 2001-04-16 | 2003-09-23 | Battelle Memorial Institute | Multilayer plastic substrates |
US20090191342A1 (en) | 1999-10-25 | 2009-07-30 | Vitex Systems, Inc. | Method for edge sealing barrier films |
US6548912B1 (en) | 1999-10-25 | 2003-04-15 | Battelle Memorial Institute | Semicoductor passivation using barrier coatings |
US6413645B1 (en) * | 2000-04-20 | 2002-07-02 | Battelle Memorial Institute | Ultrabarrier substrates |
US7198832B2 (en) * | 1999-10-25 | 2007-04-03 | Vitex Systems, Inc. | Method for edge sealing barrier films |
US20070196682A1 (en) * | 1999-10-25 | 2007-08-23 | Visser Robert J | Three dimensional multilayer barrier and method of making |
US6573652B1 (en) * | 1999-10-25 | 2003-06-03 | Battelle Memorial Institute | Encapsulated display devices |
US20100330748A1 (en) * | 1999-10-25 | 2010-12-30 | Xi Chu | Method of encapsulating an environmentally sensitive device |
US6521324B1 (en) | 1999-11-30 | 2003-02-18 | 3M Innovative Properties Company | Thermal transfer of microstructured layers |
FR2806076B1 (en) | 2000-03-08 | 2002-09-20 | Saint Gobain Vitrage | TRANSPARENT SUBSTRATE COATED WITH A POLYMER LAYER |
US6492026B1 (en) | 2000-04-20 | 2002-12-10 | Battelle Memorial Institute | Smoothing and barrier layers on high Tg substrates |
US6352744B1 (en) * | 2000-05-31 | 2002-03-05 | Owens Corning Fiberglas Technology, Inc. | Vacuum treatment of asphalt coating |
DE60132809T2 (en) * | 2000-12-21 | 2009-02-05 | Sion Power Corp., Tucson | LITHIUM ANODES FOR ELECTROCHEMICAL CELLS |
US6468595B1 (en) * | 2001-02-13 | 2002-10-22 | Sigma Technologies International, Inc. | Vaccum deposition of cationic polymer systems |
CA2352567A1 (en) * | 2001-07-06 | 2003-01-06 | Mohamed Latreche | Translucent material displaying ultra-low transport of gases and vapors, and method for its production |
US20090208754A1 (en) * | 2001-09-28 | 2009-08-20 | Vitex Systems, Inc. | Method for edge sealing barrier films |
US6888305B2 (en) * | 2001-11-06 | 2005-05-03 | Universal Display Corporation | Encapsulation structure that acts as a multilayer mirror |
US6597111B2 (en) | 2001-11-27 | 2003-07-22 | Universal Display Corporation | Protected organic optoelectronic devices |
US6765351B2 (en) * | 2001-12-20 | 2004-07-20 | The Trustees Of Princeton University | Organic optoelectronic device structures |
US7012363B2 (en) * | 2002-01-10 | 2006-03-14 | Universal Display Corporation | OLEDs having increased external electroluminescence quantum efficiencies |
US7138014B2 (en) * | 2002-01-28 | 2006-11-21 | Applied Materials, Inc. | Electroless deposition apparatus |
TW200304955A (en) * | 2002-04-05 | 2003-10-16 | Matsushita Electric Ind Co Ltd | Method and apparatus for producing resin thin film |
US6835950B2 (en) | 2002-04-12 | 2004-12-28 | Universal Display Corporation | Organic electronic devices with pressure sensitive adhesive layer |
US6897474B2 (en) | 2002-04-12 | 2005-05-24 | Universal Display Corporation | Protected organic electronic devices and methods for making the same |
US8808457B2 (en) | 2002-04-15 | 2014-08-19 | Samsung Display Co., Ltd. | Apparatus for depositing a multilayer coating on discrete sheets |
US8900366B2 (en) | 2002-04-15 | 2014-12-02 | Samsung Display Co., Ltd. | Apparatus for depositing a multilayer coating on discrete sheets |
KR100475849B1 (en) * | 2002-04-17 | 2005-03-10 | 한국전자통신연구원 | Organic electroluminescent devices having encapsulation thin film formed by wet processing and methods for manufacturing the same |
US7215473B2 (en) * | 2002-08-17 | 2007-05-08 | 3M Innovative Properties Company | Enhanced heat mirror films |
US6933051B2 (en) * | 2002-08-17 | 2005-08-23 | 3M Innovative Properties Company | Flexible electrically conductive film |
US6818291B2 (en) | 2002-08-17 | 2004-11-16 | 3M Innovative Properties Company | Durable transparent EMI shielding film |
US6929864B2 (en) * | 2002-08-17 | 2005-08-16 | 3M Innovative Properties Company | Extensible, visible light-transmissive and infrared-reflective film and methods of making and using the film |
US6890588B2 (en) * | 2002-09-05 | 2005-05-10 | Intel Corporation | Method and apparatus for applying a gel |
US6994933B1 (en) | 2002-09-16 | 2006-02-07 | Oak Ridge Micro-Energy, Inc. | Long life thin film battery and method therefor |
CN1176565C (en) * | 2002-11-25 | 2004-11-17 | 清华大学 | Package layer for organic electroluminescent device and its prepn method and application |
US7648925B2 (en) | 2003-04-11 | 2010-01-19 | Vitex Systems, Inc. | Multilayer barrier stacks and methods of making multilayer barrier stacks |
US7510913B2 (en) | 2003-04-11 | 2009-03-31 | Vitex Systems, Inc. | Method of making an encapsulated plasma sensitive device |
JP4917741B2 (en) * | 2003-05-01 | 2012-04-18 | ノードソン コーポレーション | Method for applying and drying electrode ink |
JP2005002448A (en) * | 2003-06-13 | 2005-01-06 | Tokyo Electron Ltd | Electroless plating equipment and electroless plating method |
US6998648B2 (en) * | 2003-08-25 | 2006-02-14 | Universal Display Corporation | Protected organic electronic device structures incorporating pressure sensitive adhesive and desiccant |
WO2005066667A1 (en) * | 2003-12-30 | 2005-07-21 | 3M Innovative Properties Company | Color shifting retroreflector and method of making same |
US20050269943A1 (en) * | 2004-06-04 | 2005-12-08 | Michael Hack | Protected organic electronic devices and methods for making the same |
US7292408B2 (en) * | 2004-07-30 | 2007-11-06 | Hitachi Global Storage Technologies Netherlands B.V. | Bilayer coil insulation for magnetic write heads to minimize pole recession |
US20060040091A1 (en) * | 2004-08-23 | 2006-02-23 | Bletsos Ioannis V | Breathable low-emissivity metalized sheets |
KR20130008643A (en) * | 2004-12-28 | 2013-01-22 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Prismatic retroreflective article with fluorine- or silicon-containing prisms |
US7195360B2 (en) * | 2004-12-28 | 2007-03-27 | 3M Innovative Properties Company | Prismatic retroreflective article and method |
US20060153997A1 (en) * | 2005-01-07 | 2006-07-13 | Eastman Kodak Company | Method of varying wavelengths of liquid crystals |
US7767498B2 (en) | 2005-08-25 | 2010-08-03 | Vitex Systems, Inc. | Encapsulated devices and method of making |
US8323801B2 (en) * | 2006-01-18 | 2012-12-04 | E I Du Pont De Nemours And Company | Process for forming a durable low emissivity moisture vapor permeable metallized sheet including a protective metal oxide layer |
EP2000297A1 (en) | 2006-03-24 | 2008-12-10 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
WO2007111098A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing same |
WO2007111092A1 (en) | 2006-03-24 | 2007-10-04 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
JPWO2007111076A1 (en) | 2006-03-24 | 2009-08-06 | コニカミノルタエムジー株式会社 | Transparent barrier sheet and method for producing transparent barrier sheet |
JPWO2007111074A1 (en) | 2006-03-24 | 2009-08-06 | コニカミノルタエムジー株式会社 | Transparent barrier sheet and method for producing transparent barrier sheet |
US7880371B2 (en) * | 2006-11-03 | 2011-02-01 | Danfoss A/S | Dielectric composite and a method of manufacturing a dielectric composite |
JP5519293B2 (en) | 2006-12-28 | 2014-06-11 | スリーエム イノベイティブ プロパティズ カンパニー | Nucleation layer for thin metal layer formation |
KR20150015013A (en) * | 2006-12-29 | 2015-02-09 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Method of making inorganic or inorganic/organic hybrid films |
US8084102B2 (en) * | 2007-02-06 | 2011-12-27 | Sion Power Corporation | Methods for co-flash evaporation of polymerizable monomers and non-polymerizable carrier solvent/salt mixtures/solutions |
US9660205B2 (en) * | 2007-06-22 | 2017-05-23 | Regents Of The University Of Colorado | Protective coatings for organic electronic devices made using atomic layer deposition and molecular layer deposition techniques |
US10035932B2 (en) | 2007-09-25 | 2018-07-31 | Aero Advanced Paint Technology, Inc. | Paint replacement films, composites therefrom, and related methods |
US20090162667A1 (en) * | 2007-12-20 | 2009-06-25 | Lumination Llc | Lighting device having backlighting, illumination and display applications |
CN101945965A (en) * | 2007-12-28 | 2011-01-12 | 3M创新有限公司 | Flexible package film system |
US10981371B2 (en) | 2008-01-19 | 2021-04-20 | Entrotech, Inc. | Protected graphics and related methods |
CN102084133A (en) * | 2008-04-30 | 2011-06-01 | 丹佛斯强力聚合公司 | A pump powered by a polymer transducer |
WO2009132650A2 (en) * | 2008-04-30 | 2009-11-05 | Danfoss A/S | A power actuated valve |
US8350451B2 (en) | 2008-06-05 | 2013-01-08 | 3M Innovative Properties Company | Ultrathin transparent EMI shielding film comprising a polymer basecoat and crosslinked polymer transparent dielectric layer |
EP2304069A4 (en) | 2008-06-30 | 2012-01-04 | 3M Innovative Properties Co | Method of making inorganic or inorganic/organic hybrid barrier films |
EP2340164B1 (en) * | 2008-09-26 | 2021-03-24 | Entrotech, Inc. | Methods for polymerizing films in-situ |
US9184410B2 (en) | 2008-12-22 | 2015-11-10 | Samsung Display Co., Ltd. | Encapsulated white OLEDs having enhanced optical output |
US9337446B2 (en) | 2008-12-22 | 2016-05-10 | Samsung Display Co., Ltd. | Encapsulated RGB OLEDs having enhanced optical output |
US20100167002A1 (en) * | 2008-12-30 | 2010-07-01 | Vitex Systems, Inc. | Method for encapsulating environmentally sensitive devices |
US7985188B2 (en) * | 2009-05-13 | 2011-07-26 | Cv Holdings Llc | Vessel, coating, inspection and processing apparatus |
DK2251453T3 (en) | 2009-05-13 | 2014-07-07 | Sio2 Medical Products Inc | container Holder |
US9458536B2 (en) | 2009-07-02 | 2016-10-04 | Sio2 Medical Products, Inc. | PECVD coating methods for capped syringes, cartridges and other articles |
US10544502B2 (en) | 2009-11-30 | 2020-01-28 | Xefco Pty Ltd | Functional composite garment materials |
US8460762B2 (en) | 2009-12-16 | 2013-06-11 | Ideon Llc | Electron beam curable composition for curing in a vacuum chamber |
JP5611812B2 (en) | 2009-12-31 | 2014-10-22 | 三星ディスプレイ株式會社Samsung Display Co.,Ltd. | Barrier film composite, display device including the same, and method for manufacturing the display device |
JP5611811B2 (en) * | 2009-12-31 | 2014-10-22 | 三星ディスプレイ株式會社Samsung Display Co.,Ltd. | Barrier film composite and display device including the same |
JP5290268B2 (en) * | 2009-12-31 | 2013-09-18 | 三星ディスプレイ株式會社 | Barrier / film composite, display device including the same, method for manufacturing barrier / film composite, and method for manufacturing display device including the same |
US8590338B2 (en) | 2009-12-31 | 2013-11-26 | Samsung Mobile Display Co., Ltd. | Evaporator with internal restriction |
US20110162705A1 (en) * | 2010-01-06 | 2011-07-07 | Popa Paul J | Moisture resistant photovoltaic devices with elastomeric, polysiloxane protection layer |
US8828303B2 (en) | 2010-03-31 | 2014-09-09 | Entrotech, Inc. | Methods for polymerizing films in-situ using a radiation source |
US11624115B2 (en) | 2010-05-12 | 2023-04-11 | Sio2 Medical Products, Inc. | Syringe with PECVD lubrication |
JP5564573B2 (en) * | 2010-09-03 | 2014-07-30 | 株式会社アルバック | Protective film formation method, surface flattening method |
US9878101B2 (en) | 2010-11-12 | 2018-01-30 | Sio2 Medical Products, Inc. | Cyclic olefin polymer vessels and vessel coating methods |
US9272095B2 (en) | 2011-04-01 | 2016-03-01 | Sio2 Medical Products, Inc. | Vessels, contact surfaces, and coating and inspection apparatus and methods |
EP2508646A1 (en) | 2011-04-05 | 2012-10-10 | Bayer Material Science AG | A process for multi-layer continuous roll-to-roll coating |
US8590479B2 (en) * | 2011-07-25 | 2013-11-26 | Transform Pack Inc. | Preserving seasoning flavour profiles during the manufacturing of food-seasoning sheets |
US11116695B2 (en) | 2011-11-11 | 2021-09-14 | Sio2 Medical Products, Inc. | Blood sample collection tube |
AU2012318242A1 (en) | 2011-11-11 | 2013-05-30 | Sio2 Medical Products, Inc. | Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus |
EP2792482A4 (en) | 2011-12-16 | 2015-09-02 | Konica Minolta Inc | Gas barrier film |
US8692442B2 (en) | 2012-02-14 | 2014-04-08 | Danfoss Polypower A/S | Polymer transducer and a connector for a transducer |
US8891222B2 (en) | 2012-02-14 | 2014-11-18 | Danfoss A/S | Capacitive transducer and a method for manufacturing a transducer |
US11058161B2 (en) | 2012-02-16 | 2021-07-13 | Xefco Pty Ltd | Heat reflecting composites with knitted insulation |
EP2846755A1 (en) | 2012-05-09 | 2015-03-18 | SiO2 Medical Products, Inc. | Saccharide protective coating for pharmaceutical package |
US9540526B2 (en) | 2012-10-19 | 2017-01-10 | Konica Minolta, Inc. | Gas barrier film and method for manufacturing gas barrier film |
JP6509734B2 (en) | 2012-11-01 | 2019-05-08 | エスアイオーツー・メディカル・プロダクツ・インコーポレイテッド | Film inspection method |
EP2920567B1 (en) | 2012-11-16 | 2020-08-19 | SiO2 Medical Products, Inc. | Method and apparatus for detecting rapid barrier coating integrity characteristics |
WO2014085346A1 (en) | 2012-11-30 | 2014-06-05 | Sio2 Medical Products, Inc. | Hollow body with inside coating |
US9764093B2 (en) | 2012-11-30 | 2017-09-19 | Sio2 Medical Products, Inc. | Controlling the uniformity of PECVD deposition |
US20160015898A1 (en) | 2013-03-01 | 2016-01-21 | Sio2 Medical Products, Inc. | Plasma or cvd pre-treatment for lubricated pharmaceutical package, coating process and apparatus |
US9937099B2 (en) | 2013-03-11 | 2018-04-10 | Sio2 Medical Products, Inc. | Trilayer coated pharmaceutical packaging with low oxygen transmission rate |
CN110074968B (en) | 2013-03-11 | 2021-12-21 | Sio2医药产品公司 | Coated packaging material |
EP2971227B1 (en) | 2013-03-15 | 2017-11-15 | Si02 Medical Products, Inc. | Coating method. |
CN104134756A (en) * | 2013-04-30 | 2014-11-05 | 成均馆大学校产学协力团 | Multilayer encapsulation thin-film |
US10160184B2 (en) | 2013-06-03 | 2018-12-25 | Xefco Pty Ltd | Insulated radiant barriers in apparel |
EP3693493A1 (en) | 2014-03-28 | 2020-08-12 | SiO2 Medical Products, Inc. | Antistatic coatings for plastic vessels |
JP2018523538A (en) | 2015-08-18 | 2018-08-23 | エスアイオーツー・メディカル・プロダクツ・インコーポレイテッド | Drug packaging and other packaging with low oxygen transmission rate |
US20190136095A1 (en) | 2016-09-20 | 2019-05-09 | Aero Advanced Paint Technology, Inc. | Paint Film Appliques with Reduced Defects, Articles, and Methods |
FR3104038B1 (en) * | 2019-12-04 | 2022-11-25 | Metalizz | Method of surface treatment of a three-dimensional object |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3489593A (en) * | 1965-03-24 | 1970-01-13 | Nat Res Corp | Method of sealing vacuum-deposited metal coatings |
US3467060A (en) * | 1967-10-19 | 1969-09-16 | Longacre Press Inc The | Apparatus for coating and curing epoxy resin on sheets |
USRE31532E (en) * | 1970-06-01 | 1984-03-06 | Catalyst Research Corporation | Primary cells and iodine containing cathodes therefor |
FR2245484B1 (en) * | 1973-09-28 | 1978-08-11 | Jones & Laughlin Steel Corp | |
US4098965A (en) * | 1977-01-24 | 1978-07-04 | Polaroid Corporation | Flat batteries and method of making the same |
JPS6053858B2 (en) * | 1979-02-16 | 1985-11-27 | シャープ株式会社 | Method for manufacturing electrochromic display device |
JPS57134558A (en) * | 1981-02-16 | 1982-08-19 | Fuji Photo Film Co Ltd | Production of organic vapor deposited thin film |
JPS58156848A (en) * | 1982-03-15 | 1983-09-17 | Fuji Photo Film Co Ltd | Ion selective electrode and its manufacture |
JPS5912576A (en) * | 1982-07-12 | 1984-01-23 | Nippon Denso Co Ltd | Electrode forming method of organic battery |
US4557978A (en) * | 1983-12-12 | 1985-12-10 | Primary Energy Research Corporation | Electroactive polymeric thin films |
US4551349A (en) * | 1983-12-16 | 1985-11-05 | The United States Of America As Represented By The Secretary Of The Navy | Bis(pentafluorosulfur)diacetylene polymer therefrom and preparations thereof |
US4842893A (en) * | 1983-12-19 | 1989-06-27 | Spectrum Control, Inc. | High speed process for coating substrates |
US4685415A (en) * | 1984-04-06 | 1987-08-11 | Tiegel Manufacturing Co. | Apparatus for enveloping a battery plate by a dip process |
US4844851A (en) * | 1984-08-28 | 1989-07-04 | Polyplastics Co., Ltd. | Surface metallizing method |
JPS6237247A (en) * | 1985-05-08 | 1987-02-18 | Nissan Motor Co Ltd | Nonglaring mirror |
US4772940A (en) * | 1985-05-22 | 1988-09-20 | Regents Of The University Of California | Polymer having isothianaphthene structure and electrochromic display |
JPS6289907A (en) * | 1985-06-19 | 1987-04-24 | Sumitomo Bakelite Co Ltd | Transparent conductive film united with polarizing film |
JPS62129846A (en) * | 1985-12-02 | 1987-06-12 | Dainippon Screen Mfg Co Ltd | Method and apparatus for coating photoresist |
IT1199795B (en) * | 1986-12-17 | 1988-12-30 | Ausimont Spa | PROCESS FOR THE CONSOLIDATION OF MATERIALS WITH DISCONTINUOUS STRUCTURE |
JP2692816B2 (en) * | 1987-11-13 | 1997-12-17 | 株式会社きもと | Thin primary battery |
KR970011644B1 (en) * | 1988-04-08 | 1997-07-12 | 고다까 토시오 | Coating device |
US4933129A (en) * | 1988-07-25 | 1990-06-12 | Ultrafibre, Inc. | Process for producing nonwoven insulating webs |
DE3886533T2 (en) * | 1988-09-09 | 1994-05-26 | Hydro Quebec | Method of making a thin electrode carried by a strip. |
GB8829118D0 (en) * | 1988-12-14 | 1989-01-25 | Atomic Energy Authority Uk | Electrochemical cell manufacture |
US5016991A (en) * | 1989-03-27 | 1991-05-21 | Ford Motor Company | Flexible, solid electrolyte useful in electrochromic devices |
US4997732A (en) * | 1989-03-30 | 1991-03-05 | Mhb Joint Venture | Battery in a vacuum sealed enveloping material and a process for making the same |
US4935317A (en) * | 1989-06-21 | 1990-06-19 | Mhb Joint Venture | Method for producing solid state electrochemical laminar cell utilizing cathode rolling step |
FR2653938A1 (en) * | 1989-10-26 | 1991-05-03 | Alsthom Cge Alcatel | SOLID CROSSLINKED HYBRID POLYMER ELECTROLYTE. |
US5089027A (en) * | 1990-11-26 | 1992-02-18 | Gould Inc. | Method for producing a solid electrolyte cell |
JP2948678B2 (en) * | 1991-04-24 | 1999-09-13 | 玄々化学工業株式会社 | Vacuum coating equipment |
US5131460A (en) * | 1991-10-24 | 1992-07-21 | Applied Materials, Inc. | Reducing particulates during semiconductor fabrication |
US5262253A (en) * | 1992-07-22 | 1993-11-16 | Valence Technology, Inc. | Solid electrolytes derived by polymerization of vinyl sulfonate polyalkylene oxides |
US5260095A (en) * | 1992-08-21 | 1993-11-09 | Battelle Memorial Institute | Vacuum deposition and curing of liquid monomers |
-
1992
- 1992-08-21 US US07/933,447 patent/US5260095A/en not_active Expired - Lifetime
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1993
- 1993-07-30 DK DK93918541T patent/DK0655954T3/en active
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- 1993-07-30 AT AT93918541T patent/ATE170779T1/en not_active IP Right Cessation
- 1993-07-30 WO PCT/US1993/007209 patent/WO1994004285A1/en active IP Right Grant
- 1993-08-02 US US08/100,883 patent/US5395644A/en not_active Expired - Lifetime
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1994
- 1994-11-17 US US08/341,803 patent/US5547508A/en not_active Expired - Lifetime
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DK0655954T3 (en) | 1999-06-07 |
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EP0655954B1 (en) | 1998-09-09 |
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