CN104254640A - Construct comprising metalized dicyclopentadiene polymer and method for producing same - Google Patents
Construct comprising metalized dicyclopentadiene polymer and method for producing same Download PDFInfo
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- CN104254640A CN104254640A CN201180076350.0A CN201180076350A CN104254640A CN 104254640 A CN104254640 A CN 104254640A CN 201180076350 A CN201180076350 A CN 201180076350A CN 104254640 A CN104254640 A CN 104254640A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Chemically Coating (AREA)
Abstract
The present invention comprises a method of forming a thin metal layer on a dicyclopentadiene polymer surface and to constructs comprising the metalized layer.
Description
Technical field
The present invention relates to construct comprising metallization Dicyclopentadiene (DCPD) polymer surfaces and preparation method thereof.
Background
In modern society, metalized film is very ripe existence.They are used to decorative purpose, such as balloon, hologram image, reflective paster, specular surface and physical culture card etc.Because they are to the resistance to perviousness of oxygen and moisture, they also can be used for packing through the fruits and vegetables of processing, beverage, dessert, coffee and tobacco product.They also can be used as thermal insulator in the application of such as vacuum flask to keep cold and hot, and in space suit application, keep cold and hot and prevent radiation from entering.In the electronics industry, metalized film is used for electrical condenser, resistor and other assemblies.
For pressurized vessel, due to the character that above-mentioned obstruct is strengthened, metal-coating of polymeric surface can have obvious effectiveness.That is, the metallization of the polymerization liner of pressurized vessel can improve the impermeability of liner for fluid contained in pressurized vessel significantly.When almost the complete modern light be made up of polymeric material quantizes pressurized vessel in process, this can be valuable especially.
As a nonrestrictive example, a kind of so-called IV type pressurized vessel comprises polymerization liner, and it is completely coated by thread mixture, and this mixture volume provides whole intensity of container.IV type container is the lightest in four type III pressure vessel of approval at present, but is also the most expensive.
For obvious reasons, the liner of IV type pressurized vessel is preferably made to be impermeable as far as possible for wherein contained fluid.But the existing polymkeric substance being applicable to pressure container inner lining has impermeability in various degree, and the part in them is very good, carries out metallization expection can strengthen impermeability further to the internal surface of liner.
The ancillary benefit can brought due to the metallization of polymerization pressure container inside lining comprises the inertia of enhancing, and namely liner lacks chemical reactivity for contained pressure fluid, and improves thermal insulating properties.
These benefits, are applicable to the pressurized vessel of any type comprising polymerization liner certainly.
The existing method that metallized problem is to prepare them is carried out to the polymerization liner of pressurized vessel.
The almost universal method producing metallized polymeric construct is vacuum metallization processes.Vacuum metallization processes comprises construct to metalization is placed in vacuum chamber together with the metal ingot that will be coated to the heat on construct.Electromagnetic field in room is by the surface from metallic surface Thermal release ion guide construct out.Obviously, for preparation, this process will carry out that metallized construct is less thus the metal-coating of polymeric construct that reasonably can manufacture the vacuum chamber of suitable dimension is suitable.But when this technology is used for pressurized vessel, when being intended to especially for those those containers considering compressed fluid to be carried out to sea transport, expection can have problems.This is because these containers are much bigger.
For the sea transport of fluid such as compressed natural gas (CNG), the economy of manufacture method (being transporting method substantially) is critical.The container that ocean travels can load only so many pay loads, and cost of transporting by sea reflects this fact, and the cost of the transport gross weight that calculate, namely the weight of product adds the weight of the container-ship wherein having transported product.If compared to the deadweight of pig, the net weight of product is low, then the transportation cost of the product of per unit mass becomes very expensive.This transport for compressed fluid is correct especially, routinely, in steel cylinder, transports compressed fluid, and steel cylinder extremely weighs relative to the weight of contained fluid.
Due to the appearance of type III and IV type pressurized vessel, improve this problem a little.Type III pressurized vessel is made up of thinner metal inner lining, and this thinner metal inner lining is wound with thread mixture volume, this generates the container with steel container intensity, and has obviously saved master container weight.IV type pressurized vessel mentioned above comprises polymerization liner, and this polymerization liner is enclose by compound filamentary material similarly.
Use type III and IV type container, add and these containers made the length of column shape container of very large trend-manufacture at present is 18 meters and diameter is 2.5-3 rice, consider the length of the container manufactured be more than or equal to 30 meters and diameter be more than or equal to 6 meters-make the economy optimizing sea transport compressed fluid step major step.
It is obvious that producing difficulty and the cost that can put into the vacuum chamber of the pressurized vessel of this type of huge size, can be at least very high.
Thus, required be a kind of do not relate to vacuum metallization processes metallized method is carried out to polymeric surface.The invention provides this class methods, and the construct adopting the method to prepare.
Summary of the invention
Therefore, in one aspect, the present invention relates to a kind of construct, it comprises:
Comprise at least one surface in contact of polymeric cyclopentadiene; And
Adjoin with polymeric cyclopentadiene and the first thin metal layer contacted.
Described construct also can comprise and adjoining and the second thin metal layer contacted with the first thin metal layer.
In one aspect of the invention, polymeric cyclopentadiene comprises poly-(cyclopentadiene) homopolymer.
In one aspect of the invention, poly-(cyclopentadiene) homopolymer is formed by the ring-opening metathesis polymerization (ROMP) of cyclopentadiene.
In one aspect of the invention, polymeric cyclopentadiene is the multipolymer of cyclopentadiene and one or more reaction-ity ethylene monomers, wherein, and the adhesion % by mole being enough to maintenance first metal and polymeric cyclopentadiene of the cyclopentadiene in multipolymer.
In one aspect of the invention, the first metal is selected from lower group: silver, gold, copper, nickel, tin, chromium, cadmium, zinc, cobalt and alloy thereof.
In one aspect of the invention, the first metal is silver.
In one aspect of the invention, the second metal is selected from lower group: aluminium, nickel, zinc, chromium, tin, copper and alloy thereof.
In one aspect of the invention, the second metal is selected from nickel and zinc.
In one aspect of the invention, whole construct comprises polycyclopentadiene polymkeric substance.
In one aspect of the invention, polymeric cyclopentadiene forms the one deck be arranged in construct main body, but described construct main body is manufactured by the material that can adhere to polymeric cyclopentadiene except polymeric cyclopentadiene.
Construct can be the liner of pressurized vessel.
Construct can be the assembly of pressurized vessel.
Pressurized vessel can be used for accommodating CNG.The pressure accommodating CNG can be as high as or more than 250 bar (bar).
The length of pressurized vessel can more than 6 meters.
The diameter of pressurized vessel can more than 1 meter.
One aspect of the present invention is a kind of method, and the method comprises:
There is provided the construct comprising at least one exposed surface, at least one exposed surface described comprises Dicyclopentadiene (DCPD) polymkeric substance;
With solvent cleaned polymeric cyclopentadiene surface, but not otherwise activating surface;
With the aqueous solution contactless ring pentadiene polymer surface of the salt and complexing agent that comprise the first metal;
The aqueous solution of the first metal of complexing is contacted with the aqueous solution of reductive agent on polymeric cyclopentadiene surface, wherein, deposits one deck first metal from the teeth outwards.
Described method can comprise extraly the first metal layer is contacted with the aqueous solution of bimetallic salt; Wherein
Second metal is deposited on the first metal layer in the mode of electrolysis or electroless.
In of method of the present invention, electroless ground deposition the second metal comprises the surface contact making the aqueous solution of the second metal-salt and the second complexing agent and the aqueous solution of reductive agent at the first metal layer.
In of method of the present invention, electrolytically the second metal is deposited on the first metal and comprise to the first metal layer applying negative potential; Make electronegative the first metal layer and the aqueous solution of the bimetallic salt of positively charged, the electrode manufactured by the second metal or its combine and contact.
In of method of the present invention, polymeric cyclopentadiene is made to contact to comprise with the aqueous solution of complexing salt containing the first metal aqueous solution is sprayed onto polymeric cyclopentadiene on the surface.
In of method of the present invention, the complexing salt of the first metal is made to contact to comprise with the aqueous solution of reductive agent at Dicyclopentadiene (DCPD) polymer surfaces and be sprayed onto on the surface on polymeric cyclopentadiene surface by two kinds of aqueous solutions simultaneously.
In of method of the present invention, apply negative charge and apply positive charge to the aqueous solution of bimetallic salt to comprise use battery or rectifier to the first metal layer.
In of method of the present invention, make electronegative the first metal layer contact with the aqueous solution of positively charged bimetallic salt the aqueous solution comprised positively charged bimetallic salt and be sprayed onto on the first electronegative metallic surface.
In of method of the present invention, the first metal is selected from lower group: silver, copper, nickel, tin, chromium, cadmium, zinc, cobalt and composition thereof or alloy.
In of method of the present invention, the first metal is silver.
In of method of the present invention, the second metal is selected from lower group: nickel, zinc, chromium, tin and copper.
In of method of the present invention, the second metal is selected from nickel and zinc.
In of method of the present invention, the exposed surface comprising polymeric cyclopentadiene is the liner of pressurized vessel.
In of method of the present invention, liner has the surface of rough texture.
In of method of the present invention, liner has smooth textured surface.
Described method can be used for producing construct mentioned above.
Detailed Description Of The Invention
Discuss
It should be understood that for this specification and the appended claims, the singulative relating to arbitrarily any means of the present invention comprises plural number, and vice versa, clearly obtains unless expressly stated otherwise, or from context unambiguously.
Arbitrarily approximate term used herein, such as but not limited to, close, about, to be about, substantially and basic etc., represent that the word modified by approximate term or phrase must not be accurately the values of writing, but the change that can occur to a certain degree relative to it.Its intensity of variation is much by depending on that the change that can produce has, and those skilled in the art recognize the version of modification still have the word do not modified by the term that is similar to or phrase the character, characteristic and the ability that have.As a rule, but consider discussion above, the numerical value modified herein by approximate term can change ± 10% relative to listed value, unless expressly stated otherwise.
Term used herein " optionally " and " optionally " etc. refer to realize construct design or the object of method, and the step in the feature of construct or method can exist but not be to exist.
" adjoining " used herein refers to two adjacent surfaces, and they directly contact or do not have their meetings of the words in the middle layer of another material directly to contact.
" impermeable " used herein or " not saturating " refers to a kind of material makes it that fluid substantially cannot be made to penetrate into the character in the surface of the first material formation with any significance degree.
'inertia' used herein refers to surface that a kind of material makes to be formed by this material for having the character of chemical Fails To Respond with any component of the fluid of this surface contact.
" preferably " used herein, " preferably " or " more preferably " etc. relate to the prioritizing selection that they exist when submitting present patent application to.
" fluid " used herein refers to the mixture of gas, liquid or gas and liquid.Such as, the mixture of normally gas and liquid pollutant when Sweet natural gas to extract from underground and is transported to machining center, but be not limited thereto.For purposes of the present invention, this type of mixture can form fluid.
" construct " used herein refers to the arbitrary objects of arbitrarily design or physical form, and any materials that Dicyclopentadiene (DCPD) polymkeric substance adheres to (directly or by the mode of intermediate basecoat layer) as coating by Dicyclopentadiene (DCPD) polymkeric substance or can obtain by it." fundamental construction body " refers to the construct will using method for metallising of the present invention.Fundamental construction body himself mainly can comprise Dicyclopentadiene (DCPD) polymkeric substance or it can comprise some other materials completely, such as but not limited to, other polymkeric substance, metal composite or stupalith.
" Dicyclopentadiene (DCPD) polymkeric substance " used herein refers to by the polymerization of DCPD or solidification (this term is used interchangeably herein) to obtain DCPD homopolymer (poly-(Dicyclopentadiene (DCPD)), pDCPD), or the pre-polymer formulations comprising at least 92% pure Dicyclopentadiene (DCPD) (DCPD) is cured, the polymkeric substance prepared.
At least 92% pure DCPD before " pre-polymer formulations " used herein refers to solidification and one or more reaction-ity ethylene monomers, polymerization initiator or solidifying agent are at the blend adding other desired additives arbitrarily.
Reaction-ity ethylene monomer used herein refers to containing at least one ethylene linkage, i.e. the molecule of-C=C-key, and it can react under selected polymerization condition with DCPD.Preferably at cyclenes key monomer, such as, under the existence of norbornylene.
Metal used herein " thin layer " refers to basic for atomic monolayer is to the layer of thick about 0.5 μm.
" cleaning solvent " used herein refers to the specific DCPD polymer dissolution or fully swelling that can not make for surface to metalization, but can be used in any liquid from the unwanted material of this surface removal.This class I liquid I includes but not limited to, water, alcohols, such as but not limited to, methyl alcohol, ethanol and Virahol; Ketone, such as but not limited to, acetone, methyl ethyl ketone; Hydro carbons, such as hexane, hexanaphthene, benzene, toluene etc.Because the scope that can be used for the DCPD polymkeric substance manufacturing construct is quite wide in range, often kind cannot be listed and thinkablely can be used for polymkeric substance and the solvent that can not cause negative impact to its surface, but those skilled in the art do not need too much experiment, can determine which kind of solvent meets and which kind of solvent does not meet standard herein easily.
" not otherwise activating surface " refers to the following fact: Dicyclopentadiene (DCPD) polymer surfaces of the present invention is without the need to processing with cleaning the any-mode removed except physics and chemistry pollutent except simple solvent.That is, when applying the first metal layer to Dicyclopentadiene (DCPD) polymkeric substance of the present invention, without the need to adopting the process of such as " zinc-plated " and plasma-activated (it is usually used in carrying out mirror-polishing to polymeric surface) and so on to polymkeric substance.
Therefore, in one aspect of the invention, with DCPD polymkeric substance or can adhere to DCPD polymkeric substance or adopt intermediate basecoat layer make any materials that can adhere to DCPD manufacture construct.Prime coat refers to the material layer between insertion two kinds of other materials, and wherein, priming paint can adhere to bi-material, thus is bonded together by bi-material.In content of the present invention, with the whatsoever material of obtained construct and finally must can there is metallized DCPD attachment of polymers in priming paint.Therefore, if fundamental construction body is not DCPD polymkeric substance, then using DCPD polymkeric substance as coating paint construct, to form polymer layer on one or more exposed surfaces of construct, wherein exposed surface may need to apply priming paint (primed) and can adhere to make DCPD polymkeric substance.
If fundamental construction body is Dicyclopentadiene (DCPD) polymkeric substance or other polymeric materials, then can manufactures construct with the any-mode that those skilled in the art can expect for this type of manufacture, include but not limited to, casting, molding or the solid piece from polymkeric substance are cut.
The other materials that can manufacture fundamental construction body includes but not limited to, metal, mixture and pottery etc.
Using DCPD as layer, directly or as described above can be applied to fundamental construction body together with the prime coat inserted.
Obviously, known very early metallized technology is carried out to some material.Such as, carry out patina to glass to have used more than a century to produce mirror.The method relates to from Silver Nitrate and ammonium hydroxide formation water-based silver-ammonia complex.Complex compound is contacted with glass surface, and contacts with the second solution of reductive agent silver complex being reduced into the elemental silver deposited on glass.But, find that this ancient technology one is to not being used for organic polymer.Therefore, as described above, adopt vacuum metallization processes to carry out metallized technology to organic polymeric sur-faces and in fact become standard.
Beyond expectation and be surprisingly found out that, ancient, simple, cheap metallization technology is applicable to Dicyclopentadiene (DCPD) polymkeric substance admirably.
Well-known owing to carrying out metallized technology to glass and other non-organic polymer surfaces, so only need to be briefly described it.
As glass metal easily finds to form mirror above, the electroless deposition of metal needs usually: (1) metal ion source; (2) complexing agent, to remain in stabilizing solution by metal ion; And (3) reductive agent.The most well-known example yes glass patina technique mentioned above, wherein, Silver Nitrate provides metal ion, ammonium hydroxide provides complexing agent, following various material provides reductive agent: such as but not limited to so-called " reducing sugar ", such as but not limited to glucose, fructose, glycerine aldehydes and semi-lactosi, and other aldehydes are such as but not limited to formaldehyde.The metal-salt that will reduce is depended in the selection of reductive agent, and this type of selection is well known by persons skilled in the art, and this type of materials all fall within the scope of the invention.
Solution may need pH regulator, but this is well-known for those skilled in the art equally.
Electroless plating mentioned above can be adopted deposit many metals in addition to silver, include but not limited to, gold, copper, nickel, chromium, cobalt, cadmium, iron, rubidium and tin.Also can deposit alloy, such as but not limited to, nickel-phosphorus, nickel-cobalt and nickel-X-phosphorus, wherein X is the 3rd metal.
Often kind all may need its distinctive complexing agent, and particularly its distinctive reductive agent.Complexing agent except ammonium hydroxide includes but not limited to, four nitric heterocyclic compounds, ethylenediamine tetraacetic acid (EDTA), Citrate trianion, tartrate, complexon I (nitrilotriacetic acid) and basic salt, gluconate and triethylamine.
For silver, except mentioned above those, reductive agent includes but not limited to, tartrate, dimethyamine borane, POTASSIUM BOROHYDRIDE, sodium hypophosphite, thiosulphate, hydrazine, azanol and oxoethanoic acid.
Based on content disclosed herein, select suitable complexing agent and suitable reductive agent to be well known by persons skilled in the art, and this type of assembly drop any of complexing agent and reductive agent within the scope of the invention.
In the practice of embodiments of the present invention, first with one or more solvent cleaning DCPD polymer construct or the construct of other materials being coated with DCPD polymer layer, to remove external contaminant, such as dirt, oil and moisture etc.Without the need to being further processed Dicyclopentadiene (DCPD) polymer surfaces.
Then, when existing to be kept in the solution by metal ion and to make the complexing agent of solution generally stabilization, cleaned DCPD polymer surfaces is contacted with the solution of the salt of the first metal.For purposes of the present invention, metal-salt and enveloping agent solution can be called " (first or second) metal-salt of complexing " or " complex compound of (first or second) metal-salt " simply.
There is the surface of metal-salt with surface contact or the complexing at least near surface, simultaneously or contact with the aqueous solution of reductive agent continuously.Metal complex is reduced to provide zero-valent metal, itself and DCPD attachment of polymers, namely produces the metal level of electroless deposition from the teeth outwards.
In an embodiment of the invention, can carry out spraying from the flusher separated is sprayed onto DCPD polymer surfaces by metal complex solution and reducing solution simultaneously, spray flow is led to intersect near DCPD polymer surfaces place or its, or spray from the single flusher with reservoir separately and sprinkling port, occur mix and strike polymer surfaces when two streams are gushed out from discharge end.
Depend on the texture of construct, it can be rough texture or smooth textured from the surface that the deposition of the first metal obtains, such as, the internal surface of pressure container inner lining can be smooth, this can cause basic specular surface, or coarse, this can cause the metalized surface of rough texture.
Carry out metallized DCPD polymer surfaces with the first metal can directly use, or deposition second metal can also be carried out to it.
The second metal can be deposited by identical electroless process mentioned above on the first metal, or deposition second metal can be carried out in electrochemical process, because the first metal is galvanic deposit provide required electroconductibility.
The electrodeposition process considered herein is well-known in the art, without the need to repeating.In simple terms, the metallized surface of the DCPD construct of electroless plating plating be before connected with the negative terminal (negative electrode) of direct supply, described direct supply can be battery simply, but more generally rectifier.The anode depositing to the second metal formation on the first metal layer is connected with the plus end (anode) of power supply.Be electrically connected anode and negative electrode by the mode of electrolyte solution, wherein submergence will be carried out the surface of second metallization or come this surface of shower by contact solution spray (spray).
Electrolyte solution contains wanting the metal-salt of the metal of plating and giving other ions of electrolytic conductivity of dissolving.
When applying power supply to system, metal anode is oxidized with the positively charged ion producing the metal that will deposit, and the cation transport of positively charged is to negative electrode, i.e. the metalized surface of DCPD polymer construct, there, they are reduced into zero-valent state metal and deposit on construct.
In an embodiment of the invention, the cationic solution of metal to be deposited can be prepared, and by this spray solution on metallization construct.
A current preferred purposes of method of the present invention metallizes to the internal surface of the DCPD polymer inner liner of pressurized vessel.The metallization of DCPD polymer inner liner enhances the impermeability of liner for the fluid that can accommodate in a reservoir, and improves the inertia of reaction of any component of liner and fluid.
As a non-limitative example, the pressurized vessel with metallization DCPD liner can be used for accommodating and transporting of compressed natural gas (CNG).Although pure CNG is the fluid of less responding property, it transports from its source as raw natural gas usually.Unstripped gas refers to just to be left from well, without the Sweet natural gas processed.This fluid, certainly containing Sweet natural gas (methane) itself, but usually also such as, containing liquid, condensation product, natural gasoline and liquefied petroleum gas (LPG).Also water can be there is.Also may in gaseous form or the form be dissolved in water there is other gas.These type of other gases comprise nitrogen, carbonic acid gas, hydrogen sulfide and helium.Part in them may himself be reactive, or when soluble in water may be reactive, such as produce acid when carbonic acid gas is soluble in water.
Although the component of DCPD liner to unstripped gas represents opacity and the inertia of suitable high level, can greatly strengthen these character to the metallization on PDCD surface.Therefore carrying out metallized method to the inside of pressurized vessel is very beneficial, and reason is, achieves the performance of enhancing with the minimized change of the quality of pressurized vessel (thickness of metalized surface can minimize).
In the present example, pressurized vessel as herein described can deliver various gas, and such as the direct unstripped gas from drilling well, comprises raw natural gas, such as upon compression, and raw material CNG or RCNG, or H
2or CO
2, or the Sweet natural gas (methane) of processing, or the Sweet natural gas of raw material or part processing, such as CO
2allow to be up to 14 % by mole, H
2s allows to be up to 1000ppm, or H
2and CO
2gaseous impurities, or other impurity or corrosives.But preferred purposes is CNG transport, the CNG of raw material CNG, part processing or clean CNG is processed into standard and can be transported to terminal user, such as commercial, industrial or civilian.
CNG can comprise various potential component Parts with various mixture ratio, and be partly their gas phase, other are liquid phases, or both mixing.These component Parts can comprise one or more of following compound usually: C
2h
6, C
3h
8, C
4h
10, C
5h
12, C
6h
14, C
7h
16, C
8h
18, C
9+hydro carbons, CO
2and H
2s, adds potential liquid toluene, diesel oil and octane, and other impurity/materials.
Therefore, the present invention is described by way of example completely above.Can make details to the present invention to improve, this falls within the scope of appended claims.
Claims (26)
1. a method, described method comprises:
There is provided the fundamental construction body with at least one surface, at least one surface described comprises Dicyclopentadiene (DCPD) polymkeric substance;
With solvent cleaned Dicyclopentadiene (DCPD) polymer surfaces, but not otherwise activating surface;
Providing package is containing the salt of the first metal and the first aqueous solution of complexing agent, and described complexing agent and the first metal form complex compound; And
Near the surface of Dicyclopentadiene (DCPD) polymkeric substance or its, the first aqueous solution is contacted with the second aqueous solution comprising reductive agent, thus at Dicyclopentadiene (DCPD) deposited on silicon one deck first metal.
2. the method for claim 1, is characterized in that, described fundamental construction body is substantially by Dicyclopentadiene (DCPD) polymers manufacturing, thus at least one surface described is the surface of fundamental construction body self.
3. the method for claim 1, is characterized in that, fundamental construction body is manufactured by the material except Dicyclopentadiene (DCPD) polymkeric substance, thus at least one surface described comprises the Dicyclopentadiene (DCPD) polymer layer on the surface being arranged on fundamental construction body.
4. the method as described in aforementioned any one claim, it is characterized in that, near the surface of Dicyclopentadiene (DCPD) polymkeric substance or its, make the first aqueous solution contact the surface being included in Dicyclopentadiene (DCPD) polymkeric substance with the second aqueous solution and spray two kinds of aqueous solutions simultaneously, be wherein sprayed on the surface or mixing near it.
5. the method as described in aforementioned any one claim, is characterized in that, is deposited on the first metal layer by the second metal level in the mode of electrolysis or electroless.
6. method as claimed in claim 5, it is characterized in that, second metal is deposited on the first metal in the mode of electroless and comprises: near the first metal layer surface or its, the 3rd aqueous solution comprising bimetallic salt and complexing agent is come in contact with the 4th aqueous solution comprising reductive agent.
7. method as claimed in claim 6, is characterized in that, the 3rd solution and the 4th solution are come in contact and comprises: spray two kinds of aqueous solutions at Dicyclopentadiene (DCPD) polymer surfaces place, is wherein sprayed on the surface or mixing near it.
8. method as claimed in claim 5, is characterized in that, deposited on the first metal by the second metal comprise in the mode of electrolysis:
The negative terminal of direct supply is contacted with the first metal layer;
Providing package is containing the aqueous solution of bimetallic salt, the electrode manufactured by the second metal be immersed in aqueous solution, or its combination;
The plus end of direct supply is contacted with aqueous solution;
The first metal layer is contacted with aqueous solution; And
Opening power.
9. method as claimed in claim 8, is characterized in that, described in make the first metal layer contact to comprise with aqueous solution and be sprayed onto on the first metal layer by aqueous solution.
10. method as claimed in claim 8, is characterized in that, described in make the first metal layer contact to comprise with aqueous solution and immersed in aqueous solution by the first metal layer.
11. methods as described in claim 8,9 or 10, it is characterized in that, the plus end of direct supply and negative terminal comprise battery or rectifier.
12. methods according to any one of claim 5-11, it is characterized in that, the second metal is selected from lower group: nickel, zinc, chromium, tin and copper.
13. methods as claimed in claim 12, it is characterized in that, described second metal is selected from nickel and zinc.
14. methods as described in aforementioned any one claim, it is characterized in that, described first metal is selected from lower group: silver, copper, nickel, tin, chromium, cadmium, zinc, cobalt and composition thereof or alloy.
15. methods as claimed in claim 14, is characterized in that, described first metal is silver.
16. 1 kinds of metallization constructs, it adopts the method manufacture according to any one of claim 1-15.
17. metallize construct as claimed in claim 16, and this metallization construct comprises polymerization liner.
18. constructs as claimed in claim 17, it is characterized in that, the metal level be lining with in polymerization is rough texture.
19. constructs as claimed in claim 17, it is characterized in that, the metal level be lining with in polymerization is smooth textured.
20. constructs according to any one of claim 16-19, it is characterized in that, described construct is the assembly for pressurized vessel.
21. constructs as claimed in claim 20, it is characterized in that, described construct is the liner for pressurized vessel.
22. 1 kinds of pressurized vessels, it comprises the construct according to any one of claim 16-21.
23. pressurized vessels as claimed in claim 22, this pressurized vessel is used for accommodating CNG.
24. pressurized vessels as described in claim 22 or 23, the length of this pressurized vessel is more than 6 meters.
25. pressurized vessels as described in claim 22 or 23, the diameter of this pressurized vessel is more than 1 meter.
26. 1 kinds of ships, it comprise one or more of any one of claim 22-25 the pressurized vessel that limits.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2011/071811 WO2013083175A1 (en) | 2011-12-05 | 2011-12-05 | Construct comprising metalized dicyclopentadiene polymer and method for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104254640A true CN104254640A (en) | 2014-12-31 |
Family
ID=45218711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180076350.0A Pending CN104254640A (en) | 2011-12-05 | 2011-12-05 | Construct comprising metalized dicyclopentadiene polymer and method for producing same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20150125641A1 (en) |
| EP (1) | EP2788528A1 (en) |
| CN (1) | CN104254640A (en) |
| WO (1) | WO2013083175A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9949374B2 (en) | 2013-02-08 | 2018-04-17 | Mitsubishi Electric Corporation | Electroless plating method and ceramic substrate |
| US9829153B2 (en) | 2014-09-18 | 2017-11-28 | Spencer Composites Corporation | Composite pressure vessel and method of construction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2273613A (en) * | 1939-02-17 | 1942-02-17 | Rohm & Haas | Process for preparing mirrors |
| US3533828A (en) * | 1968-04-08 | 1970-10-13 | Cosden Oil & Chem Co | Metal plating of plastic surfaces |
| US3828960A (en) * | 1972-11-10 | 1974-08-13 | Dow Chemical Co | Heat insulating container having plastic walls retaining vacuum |
| USH1807H (en) * | 1998-07-10 | 1999-10-05 | Metton America, Inc. | Organic pre-etch treatment for metal plating of cyclic olefin polymers |
| US6323296B1 (en) * | 1997-09-05 | 2001-11-27 | Mark Warner | Metathesis polymerized olefin composites including sized reinforcement material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1769802B2 (en) * | 1967-07-18 | 1976-03-11 | Cosden Oil & Chemical Co., Big Spring, Tex. (V.St.A.) | PROCESS FOR ELECTRONIC METAL COATING OF OBJECTS MADE FROM STYRENE HOMOPOLYMERS AND THEIR DERIVATIVES |
-
2011
- 2011-12-05 CN CN201180076350.0A patent/CN104254640A/en active Pending
- 2011-12-05 WO PCT/EP2011/071811 patent/WO2013083175A1/en active Application Filing
- 2011-12-05 US US14/362,573 patent/US20150125641A1/en not_active Abandoned
- 2011-12-05 EP EP11793760.7A patent/EP2788528A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2273613A (en) * | 1939-02-17 | 1942-02-17 | Rohm & Haas | Process for preparing mirrors |
| US3533828A (en) * | 1968-04-08 | 1970-10-13 | Cosden Oil & Chem Co | Metal plating of plastic surfaces |
| US3828960A (en) * | 1972-11-10 | 1974-08-13 | Dow Chemical Co | Heat insulating container having plastic walls retaining vacuum |
| US6323296B1 (en) * | 1997-09-05 | 2001-11-27 | Mark Warner | Metathesis polymerized olefin composites including sized reinforcement material |
| USH1807H (en) * | 1998-07-10 | 1999-10-05 | Metton America, Inc. | Organic pre-etch treatment for metal plating of cyclic olefin polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013083175A1 (en) | 2013-06-13 |
| EP2788528A1 (en) | 2014-10-15 |
| US20150125641A1 (en) | 2015-05-07 |
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