WO2007088217A1 - Procédé pour la métallisation de polymères d'urée et d'autres polymères - Google Patents

Procédé pour la métallisation de polymères d'urée et d'autres polymères Download PDF

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Publication number
WO2007088217A1
WO2007088217A1 PCT/ES2006/000044 ES2006000044W WO2007088217A1 WO 2007088217 A1 WO2007088217 A1 WO 2007088217A1 ES 2006000044 W ES2006000044 W ES 2006000044W WO 2007088217 A1 WO2007088217 A1 WO 2007088217A1
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WO
WIPO (PCT)
Prior art keywords
layer
acid
biting
stage
composition
Prior art date
Application number
PCT/ES2006/000044
Other languages
English (en)
Spanish (es)
Inventor
Pedro Abadia Gamon
Juan Carlos Alcorta Rubio
Original Assignee
Gabilondo Muguerza, Andres
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gabilondo Muguerza, Andres filed Critical Gabilondo Muguerza, Andres
Priority to PCT/ES2006/000044 priority Critical patent/WO2007088217A1/fr
Priority to PT2006000044A priority patent/PT2007088217W/pt
Publication of WO2007088217A1 publication Critical patent/WO2007088217A1/fr

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Classifications

    • 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
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/2033—Heat
    • 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
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • 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
    • C23C18/38—Coating with copper

Definitions

  • the present invention relates to the field of urea polymer coatings (urea-formaldehyde or bakelite) and other polymers with a metal layer with good adhesion thereof and with a decorative final appearance.
  • it refers to a process for metallizing urea polymeric parts and other polymers on an industrial level in a wet way and in a chemical-electrolytic way that essentially comprises the biting of the pieces, the chemical deposition of a layer of copper on the bitten piece and the electrolytic deposition of a layer of tin or zinc on said copper layer. In this way, a metallic layer is obtained on said polymers that has a very good adhesion.
  • biting using a biting composition based on chromic acid chromic acid and sulfuric acid in the case of ABS.
  • the neutralized serves to eliminate the chromic acid residues of the piece to be metallized. This step is essential to eliminate any trace of hexavalent chromium from the surface of the pieces since it is a poison for the subsequent treatment with catalyst. Generally in the neutralized sulphite-based salts are used, which are responsible for reducing hexavalent chromium to trivalent.
  • a good catalyzing of the surface of the piece is the key to achieve a good chemical deposition of metal.
  • the most commonly used catalyst is a colloidal solution of palladium chloride and tin (II) chloride in hydrochloric acid.
  • the colloid is 1 to 5 nm and is constituted by an inner core of palladium surrounded externally by spheres of tin (IV) hydroxide. These colloidal particles adhere in the small cavities produced in the biting stage, completely covering the surface of the piece.
  • tin chloride (IV) that surrounds, in the colloid, the palladium core. This step is carried out in the treatment with an accelerator.
  • Typical solutions are composed of chemicals that dissolve and / or complex the tin compounds (II) and (IV).
  • the most common formulations use fluoroboric acid mixed with hydrochloric acid.
  • the present inventors have discovered that the replacement of the acid copper bath in the electrolytic deposition by a tin or zinc bath has led to a strong adhesion of the metal layer to the polymeric substrate, superior even to that achieved with the "deposition system nickel chemistry + copper electrolytic deposition "used in the metallization of ABS and to the system” chemical copper deposition + copper electrolytic deposition "used in the metallization of polyester with fiberglass in printed circuits. That is, a synergistic effect is achieved by the combination of a chemical deposition of copper and an electrolytic deposition of tin or zinc.
  • the object of the present invention is to provide a process for metallizing urea polymers and other polymers by chemical-electrolytic wet route with a good final adhesion and a good decorative finish.
  • Said process essentially comprises the biting of the polymeric substrate, the chemical deposition of a copper layer on the mordented polymeric substrate and the electrolytic deposition of a tin or zinc layer on said copper layer.
  • the present invention provides a process for metallizing urea polymers and other polymers comprising the steps of: (a) biting the polymeric substrate with a biting composition comprising an acid or a mixture of acids, organic and inorganic;
  • urea polymers and other polymers refers to urea-formaldehyde polymers and other polymers such as polyurethane, polypropylene, epoxy resins, etc.
  • polymeric substrate refers to a piece or article made of said polymers.
  • a preparation of the polymeric substrate is carried out before the chemical deposition of stage (b), according to the conventional method indicated above, but varying the characteristics of the etching, both of the chemical composition employed and the conditions of work in which it is carried out.
  • the biting of step (a) of the process of the invention is carried out with a biting composition comprising an acid or a mixture of acids, organic or inorganic, not using chromic acid or any product containing salts in its composition of hexavalent chromium.
  • said biting composition may comprise a surfactant, preferably anionic, and a corrosion inhibitor. The surfactant serves to make the attack more uniform, while the inhibitor and organic acid make the attack slower and therefore also more uniform.
  • the acid concentration can vary according to the temperature and the immersion time used in the biting. In this way, at a higher temperature or longer immersion time, the acid concentration must be lowered to achieve the same effect.
  • Ia Biting composition comprises 1-80% by weight of acid. In a preferred embodiment, the biting composition comprises 40% by weight of acid.
  • the acid of the biting composition of step (a) is an inorganic acid selected from the group consisting of sulfuric, hydrochloric, hydrofluoric, phosphoric, nitric and silicic acid; an organic acid selected from the group consisting of acetic, ascorbic, benzoic, nitrobenzoic, sulfamic, tartaric, citric, formic, lactic and methanesulfonic acid; or a mixture thereof.
  • the acid of the biting composition of step (a) is sulfuric acid alone or mixed with an organic acid of those indicated above.
  • Mixtures of approximately 65-90% by weight of one or more inorganic acids may be used, the remainder being one or more organic acids.
  • the surfactants used in the biting composition can be anionic surfactants and, in particular, lauryl ether sulfates, and used in a proportion of 0.1-2% by weight.
  • the corrosion inhibitors can be compounds of the alkyl phosphate esters, lauryl mines and thioureas families, and used in a proportion of 0.1-10% by weight, the rest of the biting composition being water .
  • biting of stage (a) is carried out at a temperature between
  • the maximum permissible temperature being 70 0 C.
  • the time of stay of the pieces in the biting composition this varies depending on the working temperature.
  • the residence time of the pieces in the biting composition varies from
  • the polymeric substrate is subjected to the same stages of the traditional method of plastic metallization, as previously indicated (washing, activated, treatment with a catalyst, washing, treatment with an accelerator, washes), until you reach
  • stage (b) The chemical deposition of stage (b).
  • stage (b) In the chemical deposition of stage (b), a chemical deposition bath of copper is used (instead of the nickel bath usually used for ABS plating).
  • the minimum residence time of the polymeric substrate in the copper bath is that necessary to deposit a minimum of 0.2 ⁇ m.
  • the maximum working temperature is 60 0 C.
  • a copper layer with a thickness of 0.2-40 ⁇ m, preferably 6 ⁇ m, can be deposited.
  • the layer deposited in stage (c) is a tin layer.
  • the layer deposited in The step (c) is a layer of zinc.
  • the minimum deposition time will be necessary to deposit a minimum of 1 ⁇ m.
  • a layer of tin or zinc with a thickness of 1-40 ⁇ m, preferably 20 ⁇ m, can be deposited.
  • the electrolytic deposition by one of tin or zinc, is one of the reasons for achieving the strong adhesion of the metal to the polymer.
  • the tin bath is a process normally used in the sector of metal coatings and has a low cost compared to other baths of other metals.
  • tin bath is preferred over zinc, since it is a nobler metal and gives the polymeric substrate a better final appearance.
  • stage (c) After the tin or zinc coating of stage (c), it is possible to apply back layers of another metal by any conventional chemical or electrolytic method.
  • the process further comprises an additional electrolytic or chemical deposition stage of at least one other metallic layer.
  • said additional metal layer is a layer of copper, nickel, gold, silver, chromium, zinc, rhodium, or one of its alloys, or mixtures thereof. These alloys include brass and bronze, among others.
  • the final layer of the required metal will be given according to the desired finish. In some cases it will be necessary to apply several layers. Thus, for example, to give a final finish of brass, chrome, gold or silver, it is necessary to apply a previous layer of nickel.
  • the process of the invention comprises an additional stage of finishing, preferably of oxidized, lacquered, waxed or oiled.
  • urea polymeric part (polymeric substrate) is subjected to the following stages of the total process:
  • Biting of the piece it is carried out by means of a biting composition comprising an acid or a mixture of acids, organic or inorganic, as previously indicated.
  • said composition is formed by weight of 35% inorganic acid, 5% organic acid, 0.2% ammonium surfactant and 1% inhibitor, the rest being water.
  • Catalyst A commercial product is used on purpose for this purpose, consisting of a mixture of tin and palladium chlorides in hydrochloric acid. The piece is immersed in it for 5-10 minutes at a temperature between 15 and 35 0 C.
  • Accelerator A commercial product suitable for this purpose, consisting of fluorine salts, is used. The piece is immersed in it for 30-90 seconds at a temperature between 15 and 35 0 C.
  • Tin coating for example, from an acidic pH solution, or zinc coating from an acidic or alkaline solution. With a deposition time to deposit a minimum of 1 ⁇ m.
  • any other metal backing can be applied chemically or electrolytically.
  • the pieces can be finished with the following finishes: - copper
  • baths normally used in the surface coatings sector are used for this purpose.
  • the metallized polymeric piece can be subjected to a final stage of finishing such as oxidized, etched, lacquered, oiled, etc., as previously indicated.
  • a mordanting composition was formulated with the following concentrations by weight: 40% sulfuric acid and 5% citric acid. In addition, 0.2% sodium lauryl sulfate was added as an anionic surfactant and 1% thiourea as an inhibitor, the rest was completed with net water. Ia solution was heated to a temperature of between 35 and 40 0 C and immersed therein for 2 hours parts.
  • the pieces were immersed for 5 minutes in a tin / palladium catalyst bath at a temperature between 20 and 30 0 C.
  • the bath was composed by volume of 1% of a commercial product suitable for this purpose and 20% of 35% hydrochloric acid, the rest was completed with deionized water.
  • the pieces were immersed for 60 seconds in an accelerator bath at room temperature.
  • the bath was composed by volume of 1% of a commercial product suitable for this purpose composed of fluorine salts, as previously indicated and 20% of 35% hydrochloric acid, the rest was completed with network water.
  • Parts were washed thoroughly with running water. The pieces were immersed in a bath of chemical copper deposition for 30 minutes at a temperature between 35 and 40 0 C.
  • the bath was composed essentially of copper sulfate, formaldehyde as reductant, EDTA as sequestering and soda to adjust pH, all dissolved in deionized water.
  • the pieces were immersed in a neutralizing solution formed with 5% sulfuric acid for 60 seconds and at room temperature.
  • the pieces were immersed for 20 minutes at a temperature between 20 and 25 0 C in an acid bath tin electrolytic composition by weight 3% of tin sulfate and 15% sulfuric acid, and a range of organic products suitable for this bath in order to make the tin coating bright (polyethylene glycol and benzalacetone).
  • Urea metallic copper oxide a layer of copper was deposited that was oxidized with a suitable product for it and then gratified to give an old look. After the engraving, the piece was lacquered. The final appearance was bright pink with black trim.
  • Urea metallized brass oxide it was deposited from a layer of copper and then another layer of brass that was oxidized with a suitable product for it and then gratified to give an old look. After the engraving, the piece was lacquered. He final appearance was bright yellow with black trim.
  • Urea metallic silver oxide a layer of silver was deposited that was oxidized with a suitable product for it and then gratified to give an old look. After the engraving, the piece was lacquered. The final appearance was bright white with black trim.
  • the adhesion test was also performed, obtaining a total adhesion result. For this, bending tests of the pieces were carried out until they were broken, from the cascade part it was tried, with a knife blade, to separate the metal layer from the base material, which was impossible. The test was also performed according to the UNE-EN ISO 2409 standard of the "Lattice cutting test", obtaining the classification 0, the maximum granted according to this test.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un procédé destiné à la métallisation par voie humide chimique-électrolytique de polymères d'urée et d'autres polymères. Ce procédé consiste: (a) à attaquer le substrat polymérique avec une composition de mordançage comprenant un acide ou un mélange d'acides organiques ou inorganiques; (b) à déposer par voie chimique une couche de cuivre sur le substrat polymérique attaqué; et (c) à déposer par voie électrolytique une couche d'étain ou de zinc sur la couche déposée à l'étape (b). Le procédé peut également comprendre une étape supplémentaire de dépôt électrolytique ou chimique d'au moins une autre couche métallique et/ou une étape supplémentaire de finissage, telle qu'une étape d'oxydation, de laquage, de cirage ou d'huilage. Le procédé permet d'obtenir une couche métallique sur lesdits substrats polymériques, qui présente une très bonne adhérence et un aspect final qui peut servir de finition décorative.
PCT/ES2006/000044 2006-02-01 2006-02-01 Procédé pour la métallisation de polymères d'urée et d'autres polymères WO2007088217A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/ES2006/000044 WO2007088217A1 (fr) 2006-02-01 2006-02-01 Procédé pour la métallisation de polymères d'urée et d'autres polymères
PT2006000044A PT2007088217W (pt) 2006-02-01 2006-02-01 Processo para metalizar polímeros de ureia e outros polímeros.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2006/000044 WO2007088217A1 (fr) 2006-02-01 2006-02-01 Procédé pour la métallisation de polymères d'urée et d'autres polymères

Publications (1)

Publication Number Publication Date
WO2007088217A1 true WO2007088217A1 (fr) 2007-08-09

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PT (1) PT2007088217W (fr)
WO (1) WO2007088217A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011025753A1 (fr) 2009-08-24 2011-03-03 Lacks Industries, Inc. Finition de surface décorative et son procédé de formation
CN104264135A (zh) * 2014-09-25 2015-01-07 湖南大学 一种铝及其合金镀前催化活化预处理剂

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3915664A (en) * 1971-01-20 1975-10-28 Hoechst Ag Moulded article
US4227963A (en) * 1978-09-07 1980-10-14 Standard Oil Company Chemical etching of polymers for metallizing utilizing an aqueous sulfuric-carboxylic acid etchant
US4639380A (en) * 1985-05-06 1987-01-27 International Business Machines Corporation Process for preparing a substrate for subsequent electroless deposition of a metal
US5302415A (en) * 1992-12-08 1994-04-12 E. I. Du Pont De Nemours And Company Electroless plated aramid surfaces and a process for making such surfaces
US6045680A (en) * 1996-05-30 2000-04-04 E. I. Du Pont De Nemours And Company Process for making thermally stable metal coated polymeric monofilament or yarn

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3915664A (en) * 1971-01-20 1975-10-28 Hoechst Ag Moulded article
US4227963A (en) * 1978-09-07 1980-10-14 Standard Oil Company Chemical etching of polymers for metallizing utilizing an aqueous sulfuric-carboxylic acid etchant
US4639380A (en) * 1985-05-06 1987-01-27 International Business Machines Corporation Process for preparing a substrate for subsequent electroless deposition of a metal
US5302415A (en) * 1992-12-08 1994-04-12 E. I. Du Pont De Nemours And Company Electroless plated aramid surfaces and a process for making such surfaces
US6045680A (en) * 1996-05-30 2000-04-04 E. I. Du Pont De Nemours And Company Process for making thermally stable metal coated polymeric monofilament or yarn

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011025753A1 (fr) 2009-08-24 2011-03-03 Lacks Industries, Inc. Finition de surface décorative et son procédé de formation
US8632864B2 (en) 2009-08-24 2014-01-21 Lacks Industries, Inc. Decorative surface finish and method of forming same
CN104264135A (zh) * 2014-09-25 2015-01-07 湖南大学 一种铝及其合金镀前催化活化预处理剂

Also Published As

Publication number Publication date
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