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WO2003101733A1 - Procede pour realiser une couche de liaison polymerique sur une surface metallique - Google Patents

Procede pour realiser une couche de liaison polymerique sur une surface metallique Download PDF

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Publication number
WO2003101733A1
WO2003101733A1 PCT/US2003/017603 US0317603W WO03101733A1 WO 2003101733 A1 WO2003101733 A1 WO 2003101733A1 US 0317603 W US0317603 W US 0317603W WO 03101733 A1 WO03101733 A1 WO 03101733A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal surface
tie layer
cleaning
metal
duty cycle
Prior art date
Application number
PCT/US2003/017603
Other languages
English (en)
Inventor
Jack R. Frautschi
Original Assignee
Western Life Sciences, Llc
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 Western Life Sciences, Llc filed Critical Western Life Sciences, Llc
Priority to US10/473,648 priority Critical patent/US20040234703A1/en
Priority to AU2003243389A priority patent/AU2003243389A1/en
Priority to EP03756391A priority patent/EP1531989A4/fr
Publication of WO2003101733A1 publication Critical patent/WO2003101733A1/fr

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Classifications

    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • 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
    • B05D2202/00—Metallic substrate
    • 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
    • B05D3/14—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 electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment

Definitions

  • the present invention relates to the field of plasma deposition of organic films on substrates and, more particularly, to a method for the deposition of an organic film tie layer on a metal surface using radio frequency plasma deposition.
  • Plasma deposition has been used to create a very tight adhesion, via a chemical bond, between the deposited film and a nonmetal polymer substrate, particularly for medical application.
  • this process allows nonmetal substrates to be coated without exposing them to solvents, high temperatures, or radiation.
  • Films deposited by this technique display many desirable characteristics including ease of preparation, coating uniformity, conformal coverage of complex substrates, and the ability to generate unique chemistries.
  • the deposited films generally do not penetrate into the substrate and therefore do not significantly change the mechanical properties from that of the unmodified substrate.
  • the films are usually free of leachable components and can be designed to prevent leachable components in the substrate from diffusing out.
  • Plasma deposition of film on metal substrate has not been as successful as with nonmetal substrates.
  • Known methods of plasma deposition of a film on a metal substrate involve applying a hydrocarbon residue undercoat to a metal substrate by plasma deposition.
  • a photoactive hydrophilic polymer is then deposited on the hydrocarbon residue coating and activated by ultraviolet light.
  • the hydrocarbon residue coating acts as a tie layer between the hydrophilic polymer and the metal substrate by providing C-C bonds (carbon-carbon single bond) for the covalent linking of the hydrophilic polymer to the tie layer.
  • Another approach that has been used has been to apply fluorinated coatings such as teflon on metal substrates. These present methods provide coatings on metal surfaces that are excessively thick, have relatively low adhesion and elasticity, and can crack under stress. In addition, when such coatings are scratched fluids can penetrate through the film to the interface of the film and the metal, producing film delamination.
  • the present invention provides a process for coating substrates, including metals, with a tie layer.
  • the tie layer can have functional groups on its surface for the chemical attachment of a second coating, or can act on its own by providing lubricity or blood compatibility, or both to the underlying metal.
  • the metal substrate is first cleaned with solvent, then cleaned with oxygen plasma, and then sputter cleaned with argon plasma.
  • Polymer deposition can be produced under pulsed conditions using a duty cycle where the duty cycle is reduced over time. These steps allow the film on the substrate surface to transition from a more rigid highly adhesive hydrocarbon to an elastic polymer similar to a naturally polymerized polymer. This transition in film properties increases the mechanical strength of the polymer film by reducing the occurrence of stress risers within the film, when placed under mechanical loads or stresses.
  • An advantage of the present invention is a simple plasma deposition method for producing a tightly bound, strong, elastic polymer film on a metal substrate.
  • Another advantage of the present invention is a method of sputter cleaning a metal surface to remove loosely adherent metal oxide and facilitate functionalization of the metal surface.
  • Another advantage of the present invention is a method of polymer deposition under pulsed conditions using a duty cycle, where the duty cycle is reduced over time, and the off time is minimized and kept constant to keep the plasma lit at low plasma powers.
  • Another advantage of the present invention is the use of a plasma system composed of two separate plasma generating units comprising a top coil and a bottom biased chuck, the chuck being used for sputtering and to enhance deposition during plasma generation by the top coil.
  • Another advantage of the present invention is a method for producing polymer films on a metal surface which provide a variety of surface properties, including lubricious and/or blood compatible properties.
  • Fig. 1 shows a diagram of the steps of the method of the present invention.
  • Fig. 2 shows a diagram of the chemical conformation of the polybutadiene tie layer.
  • Fig. 4 shows pictures obtained under optical microscopy of coated metal surfaces bent 90° and soaked.
  • Fig. 5 shows pictures obtained under scanning electron microscopy of coated metal surfaces flexed and soaked.
  • Fig. 6 shows pictures obtained under scanning electron microscopy of a coated metal surface containing a 25 ⁇ m-wide scratch.
  • Fig. 7 shows pictures obtained under scanning electron microscopy of a coated metal surface containing a 50 ⁇ m-wide scratch.
  • Fig. 1 shows the method 10 of the present invention used to create a very adherent tie layer to a metal surface.
  • the plasma system consisted of two separate plasma generating units, a high density plasma source system (upper coil) and a lower chuck bias power source system, each having a power source at a radiofrequency (RF) of 13.56 kHz.
  • the chuck is used for sputtering and to enhance deposition during plasma generation by the top coil.
  • Both of the plasma generators contained an impedance matching network to tune the plasma.
  • step 11 the metal surface is cleaned with solvent to remove surface contaminants.
  • step 12 the metal surface is cleaned with plasma oxygen to remove remaining contaminants.
  • step 13 the metal surface is argon sputter cleaned to remove loosely adherent oxidized metal and thus promote bonding to the native metal.
  • the alternating e-field of the lower chuck is perpendicular to the lower chuck, attracting both positive and negative ions causing them to bombard the sample at a high energy.
  • step 14 the metal surface is functionalized. Chemically reactive intermediates are bonded to the metal to create a direct chemical binding between the metal and polymer coating.
  • Oxygen is conveniently used to create oxides on the surface of the metal.
  • other gases such as NH 3 , H 2 O, CO , H 2 O 2 , etc. may be utilized to create functional groups, to enhance the binding strength of the metal-polymer bond.
  • the functional groups created on a metal surface like NHx, OH, OOH, CO ⁇ , O , etc. may allow the depositing polymer to form a chemical bond with the metal, which otherwise would not be formed, or to form a stronger more stable chemical bond with the metal.
  • Step 15 is the polymer deposition of the butadiene polymer tie layer. Deposition occurs under pulsed conditions, where the duty cycle is reduced over time.
  • the off time of the pulse is kept at 40 milliseconds (ms). This is accomplished by increasing the pulse frequency as the duty cycle is reduced, consequently keeping the plasma off time to a minimum, so that the plasma will remain lit at very low average powers.
  • a leakage current (about 0.1 W) that is applied to the lower chuck bias electrode enhances the rate of deposition by causing a small attraction of charged polymer particles and other charged moieties.
  • the leakage current is turned off during plasma deposition at very low RF source powers.
  • the duty cycle may be modified to provide, for example: 1) thicker polymer films by increasing the time at each duty cycle, or 2) less elastic polymer films by not depositing at the low duty cycles.
  • a quench with the monomeric depositing moiety e.g. butadiene
  • Fig. 2 shows the polybutadiene-vinyl conformation of the tie layer formed by the method of the present invention.
  • Samples from tie layers created as detailed in Fig. 1 were analyzed with the Grazing Angle FTIR-ATR. The Grazing Angle
  • FTIR-ATR provides 100X the chemical sensitivity when compared to standard FTIR-ATR, so the outermost monolayer can be sampled and recorded.
  • the plasma deposited polybutadiene by the method of the present invention produces polymers composed of the vinyl conformation (>85%).
  • a stainless steel wire was washed successively for 3 minutes with methylene chloride, isopropanol, and deionized water, and then air dried (step 11).
  • the wire was then cleaned with plasma oxygen to remove remaining contaminants, using inductive plasma at 200W, 50 Torr, 20 seem (standard cubic centimeters) O 2 , 30 seconds (step 12).
  • the wire was then argon sputter cleaned to remove loosely adherent oxidized metal and thus promote bonding of the tie layer to the native metal.
  • Capacitive plasma was used with the lower chuck bias electrode at 60 W, 100 mTorr, 20 seem argon, 60 seconds (step 13).
  • butadiene quenching allows any remaining reactive intermediates like radicals to react with butadiene molecules and thereby create a more chemically stable film (step 15).
  • tape test ASTM D3359-97
  • the bent coated wire was straightened, placed in 37 °C flowing water for 10 minutes, removed from the water and bent 90°, and placed back in the 37 °C flowing water for 20 hours.
  • Fig. 4 shows the results of this test using optical microscopy (20X magnification).
  • Fig. 5 shows the results of this study using scanning electron microscopy.
  • the sample with the butadiene tie layer no cracks were evident in the surface film.
  • the sample with the parylene tie layer 2-6 ⁇ m-wide cracks were observed which could allow water to reach the metal surface. In such a case, water will wick along the metal surface causing delamination. If coating fragments were removed from the parylene tie layer the result would be emboli formation in the blood stream.
  • the butadiene coating of the present invention would be expected to be safer for in vivo use compared to the parylene coating.
  • the results show that the method of the present invention produces polymer coatings that are highly adhesive and highly elastic.
  • a scratch was made on a flat piece of stainless steel, the scratch being representative of damage produced by a sharp surgical tool or by crystalline plaque in calcific blood vessels.
  • the metal samples were bent 90°, incubated for 10 minutes in 37°C flowing water, then bent 180° in the opposite direction, and placed in the 37 °C flowing water/saline for 20 hours.
  • the samples were then evaluated by scanning electron microscopy (350 X magnification).
  • Fig. 6 shows the results of a 25 ⁇ m-wide scratch
  • Fig. 7 shows the results of a 50 ⁇ m- wide scratch. In both cases there was no cracking or delamination of the coating and no evidence of water migration along the metal/polymer boundary.
  • Pharmacologic agents such as, for example, heparin or antibiotics, can be delivered from secondary coatings attached to the tie layers of the present invention. It will be understood that various changes in the details, materials, and arrangements of the parts which have been described and illustrated above in order to explain the nature of this invention may be made by those skilled in the art without departing from the principle and scope of the invention as recited in the following claims.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne un procédé pour réaliser une couche de liaison polymérique sur une surface métallique comprenant les étapes suivantes : nettoyage de la surface métallique au solvant ; nettoyage de la surface métallique par plasma à oxygène ; nettoyage par pulvérisation de la surface métallique à l'argon au moyen d'une unité de génération de plasma à polarisation de mandrin basse ; fonctionnalisation de la surface métallique et dépôt de la couche de liaison sur la surface métallique par dépôt activé par plasma RF dans des conditions pulsées d'un cycle de travail, le cycle de travail diminuant dans le temps. Ce procédé produit une couche de liaison chimiquement liée à la surface métallique. Ainsi, cette couche de liaison présente une résistance de liage au métal et une élasticité élevées, la rendant très résistante aux craquelures, aux rayures, à la délamination et à l'effet de mèche. La couche de liaison peut présenter à sa surface des groupes fonctionnels pour la fixation chimique d'un deuxième revêtement ou peut fournir seule un pouvoir lubrifiant ou une compatibilité sanguine au métal sous-jacent.
PCT/US2003/017603 2002-06-04 2003-06-04 Procede pour realiser une couche de liaison polymerique sur une surface metallique WO2003101733A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/473,648 US20040234703A1 (en) 2002-06-04 2003-06-04 Method of forming a polymer layer on a metal surface
AU2003243389A AU2003243389A1 (en) 2002-06-04 2003-06-04 Method of forming a polymer tie layer on metal surface
EP03756391A EP1531989A4 (fr) 2002-06-04 2003-06-04 Procede pour realiser une couche de liaison polymerique sur une surface metallique

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US38569902P 2002-06-04 2002-06-04
US60/385,699 2002-06-04
US44678103P 2003-02-12 2003-02-12
US60/446,781 2003-02-12

Publications (1)

Publication Number Publication Date
WO2003101733A1 true WO2003101733A1 (fr) 2003-12-11

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ID=29715379

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/017603 WO2003101733A1 (fr) 2002-06-04 2003-06-04 Procede pour realiser une couche de liaison polymerique sur une surface metallique

Country Status (3)

Country Link
EP (1) EP1531989A4 (fr)
AU (1) AU2003243389A1 (fr)
WO (1) WO2003101733A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10104770B2 (en) 2013-04-09 2018-10-16 3M Innovative Properties Company Touch panel, preparing method thereof, and Ag—Pd—Nd alloy for touch panel

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6080488A (en) * 1995-02-01 2000-06-27 Schneider (Usa) Inc. Process for preparation of slippery, tenaciously adhering, hydrophilic polyurethane hydrogel coating, coated polymer and metal substrate materials, and coated medical devices

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5002794A (en) * 1989-08-31 1991-03-26 The Board Of Regents Of The University Of Washington Method of controlling the chemical structure of polymeric films by plasma
US5618619A (en) * 1994-03-03 1997-04-08 Monsanto Company Highly abrasion-resistant, flexible coatings for soft substrates
US5846649A (en) * 1994-03-03 1998-12-08 Monsanto Company Highly durable and abrasion-resistant dielectric coatings for lenses

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6080488A (en) * 1995-02-01 2000-06-27 Schneider (Usa) Inc. Process for preparation of slippery, tenaciously adhering, hydrophilic polyurethane hydrogel coating, coated polymer and metal substrate materials, and coated medical devices

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1531989A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10104770B2 (en) 2013-04-09 2018-10-16 3M Innovative Properties Company Touch panel, preparing method thereof, and Ag—Pd—Nd alloy for touch panel

Also Published As

Publication number Publication date
EP1531989A4 (fr) 2006-11-29
AU2003243389A1 (en) 2003-12-19
EP1531989A1 (fr) 2005-05-25

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