WO2008010747A1 - Procédé de production d'une surface rugueuse sur un substrat - Google Patents

Procédé de production d'une surface rugueuse sur un substrat Download PDF

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Publication number
WO2008010747A1
WO2008010747A1 PCT/SE2006/000894 SE2006000894W WO2008010747A1 WO 2008010747 A1 WO2008010747 A1 WO 2008010747A1 SE 2006000894 W SE2006000894 W SE 2006000894W WO 2008010747 A1 WO2008010747 A1 WO 2008010747A1
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WO
WIPO (PCT)
Prior art keywords
coating
substrate
pressure
metallic substrate
metallic
Prior art date
Application number
PCT/SE2006/000894
Other languages
English (en)
Inventor
Anna Andersson
Mikael Schuisky
Original Assignee
Sandvik Intellectual Property Ab
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 Sandvik Intellectual Property Ab filed Critical Sandvik Intellectual Property Ab
Priority to PCT/SE2006/000894 priority Critical patent/WO2008010747A1/fr
Publication of WO2008010747A1 publication Critical patent/WO2008010747A1/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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides

Definitions

  • the present invention relates to a method according to the pre-characterizing portion of claim 1.
  • Such a method is known from for example JP 1129958, wherein a method for evaporating Ti is disclosed.
  • the source is evaporated by the actuation of an electron gun, thereby forming a titanium nitride film on a surface of a material, such as steel grade SUS 304, to be treated.
  • Metallic laminates and fiber metal laminates are today used in several different applications such as aerospace applications and armor applications.
  • the main reason for using this type of laminate structures in aerospace applications is the reduction of weight.
  • laminate structures have high mechanical strengths, good fatigue strengths, works as thermal barriers, as well as shock and damage barriers. These two latter features are also the reason to use these types of laminates in armor applications since the multilayer laminate structure will work as a shock absorber and limit the impact of a projectile.
  • adhesion strength of stainless steel towards organic adhesives is however not always sufficient during use in some applications.
  • insufficient adhesive strength may lead to micro cracks or tendencies of delaminations at the interface between the fiber layers and the metal foils. This may be detrimental for the strength, and thereby the operation conditions and the service life, of the laminate.
  • the adhesion strength may also cause problems in certain decorative metallic laminates and painted stainless steels exposed to severe external mechanical stress.
  • the difference in the coefficient of thermal expansion between steel and organic plastics is one cause for adhesion problems.
  • Another approach is to apply a surface coating to the stainless steel that increases the wetting of the adhesive. This may be a simpler one-step method that with the application of a high surface energy coating to the stainless steel can create a very strong bond between steel and adhesive.
  • the object of the present invention is to provide a steel substrate with improved surface properties wherein said substrate is suitable for use in metallic laminates and fiber metal laminates (FML). More specifically, the object of the present invention is to provide a steel substrate with improved adhesiveness to organic adhesives.
  • a metallic substrate is provided with at least one coating layer comprising Ti by means of electron beam evaporation wherein the pressure in the coating chamber is increased at least 10 times, preferably at least 100 times, from normal pressure in the coating chamber.
  • a metallic substrate can be provided with a coating having an excellent adherence to the substrate as well as an increased adherence to for example a further coating of a paint or lacquer, or adjacent material in a laminate structure through an adhesive.
  • Figure 1 illustrates a coated substrate produced in accordance with the present invention.
  • Figure 2 illustrates a coated substrate, having several coating layers, produced in accordance with the present invention
  • Figure 3 illustrates a metallic laminate produced in accordance with the present invention.
  • Figure 4 illustrates a coated substrate produced in accordance with the present invention with an additional coating layer of a lacquer.
  • Figure 5 illustrates an alternative metallic laminate produced in accordance with the present invention.
  • Figure 6 illustrates the change in contact angle of four samples with TiN x coatings, with increasing pressure in the coating chamber.
  • Figure 7 illustrates the estimated surface energy of four samples with TiN x coatings.
  • Figures 8a-d show SEM photographs of TiN x coatings applied at different nitrogen pressures.
  • Figures 9a-h show SEM photographs of Ti coatings applied at different pressures and wherein the pressure is regulated with Ar.
  • Electron beam evaporation is a physical vapor deposition process wherein electrons are directed towards a source of material which is to be evaporated and thereby transferred to a substrate which is to be coated with the material. The kinetic energy of the electrons is transformed to heat at impact with the material causing the material to evaporate. Evaporation usually takes places under reduced atmosphere, i.e. vacuum. The specific pressure is adapted to the material to be evaporated.
  • Electron beam evaporation can be used both as a batch process and a continuous process.
  • An advantage with a continuous process is that the coating can be performed at a high production rate. Substrate speeds of 25-75 meters per minute are not unusual. This allows a comparatively low substrate temperature since the substrate passes the coating chamber fairly quickly, causing minimal risk of distortion of the substrate as a result of the comparatively low thermal load during the deposition.
  • a continuous process makes it possible to coat long objects, such as substrates up to 20 km long. A continuous electron beam evaporation process is therefore recommendable in order to produce large scale objects in a cost effective manner.
  • a surface of a substrate 1 is coated by electron beam evaporation with at least one coating layer 2 comprising Ti, as shown in Figure 1.
  • a coating having a high surface area A can be achieved.
  • the pressure in the chamber may be increased before the actual coating process begins, or during the coating process.
  • the pressure may also be regulated during the coating process to ensure the desired gas to vapor ratio.
  • the density of the coating decreases with increasing pressure in the chamber during coating. If low pressures are use in the evaporation process usually dense coatings are formed. The reason for this is simple, the energy of the evaporated metal, in the present case titanium, will less likely collide with gas molecules before condensation on the substrate surface. At any collision of the vapor material on its way to the surface of the substrate it will lose energy by momentum transfer. This will give the metal vapor more reserved energy when it condensates on the surface to arrange the coating structure i.e. densify the coating. However, if the metal vapor has low energy when it impacts with the substrate surface it will less likely have enough energy to densify the coating i.e. a low density coating with rougher sub-micrometer morphology is formed.
  • the pressure in the coating chamber is preferably increased at least 100 times, most preferably at least 1000 times, compared to normal coating pressure.
  • the possible maximum pressure is mainly limited by the equipment used.
  • Suitable metallic substrates are substrates of alloys based on any of the elements Fe, Al, Ti, Mg, Ni and Cu, preferably stainless steel. By utilizing alloys based on these elements, a low weight metallic laminate may be produced which is suitable in applications requiring low weight structures having high mechanical strength. Examples of such applications are as constructional parts or body sheets for vehicles, such as cars, trucks, ships and aircrafts. Also, if low thermal expansion is required for the intended final product a suitable substrate may be Fe64Ni36, also known under the trade name Invar, which is a material with very low thermal expansion.
  • the substrate may be in form of a strip, foil, tube, wire, plate, bar etc. However, it may also be in more complex shapes. Preferably the substrate is in the shape of a strip due to the intended use in fiber metal laminates or metallic laminates.
  • the form of a strip also enables the use of a continuous coating process, which is beneficial for inter alia economical reasons as mentioned earlier.
  • the coating metal is Ti, or an alloy based on Ti. This renders a coating comprising Ti.
  • Ti is preferably chosen as the coating metal since it is a reactive metal which provides excellent adhesion to the substrate even if the coating layer should be highly porous.
  • a coating based on Ti is ductile which enables further processing, such as bending, stretching or stamping, of the coated substrate without causing any spalling or cracking of the coating. Titanium metal is easily evaporated by electron beam evaporation and the pressures of the deposition process can be carefully monitored.
  • the pressure in the deposition chamber is increased by introduction of an appropriate volume of gas into the deposition chamber.
  • the selection of gas can be tuned to fit the wanted process.
  • the introduced gas can be purified air, oxygen, ozone or any other oxidizing gas.
  • the gas can be any nitrogen containing gas, such as pure nitrogen, ammonia, hydrazine or even mixtures of N 2 and H 2 .
  • a non-stoichiometric metal oxide or nitride coating is provided on the surface of the steel.
  • the coating produced according to the method has a micro crystalline or an amorphous structure with sub-micrometer sized grains and is substantially hydrophilic.
  • the contact area between the coated substrate and an adjacent coating of an adhesive is increased whereby the adherence is improved.
  • a surface with sub-micrometer sized grains creates capillary forces in the surface pores and grain boundaries, which in turn improves the adherence of the surface further. This formed rough sub- micrometer size morphology will therefore be very good for adhesion of a laminate layer on to the coated steel substrate.
  • the coated substrate is treated further.
  • the coated substrate may be subjected to a heat treatment to increase the mechanical strength of the substrate.
  • the coated substrate may also be subjected to an oxidation step, preferably at an elevated temperature, directly after the coating step in order to provide the surface with a fully oxidized surface. This may for example be beneficial in applications requiring anti-bacterial behavior, such as surfaces of Ti ⁇ 2 for use in food processing or medical devices.
  • the substrate is preferably cleaned in a proper way to remove any oil residue or the like from previous manufacturing steps, such as rolling or drawing, before coating in order to achieve a good adhesion of the coating to the substrate.
  • a suitable method may for example be a degreasing bath followed by ion assisted etching.
  • the ion assisted etching is preferably conducted in line with the coating process.
  • this step may preferably be conducted in the same chamber as the coating process if the equipment to be used for the coating process so permits.
  • the electron beam evaporation process according to the present disclosure is not activated, such as by means of e.g. plasma, since this normally produces more dense coatings which would not give a rough enough surface morphology.
  • the substrate is preferably not subjected to elevated temperatures directly before or during coating since a hot substrate may facilitate formation of bigger crystals in the coating in addition to causing structural changes of the substrate.
  • the temperature of the substrate is kept below 300 0 C.
  • the metal to be evaporated is Ti and the pressure in the chamber is increased by means of nitrogen containing gas.
  • the normal pressure in the chamber is approximately 10 "6 mbar.
  • the pressure in the chamber is increased to at least 5 * 10 "5 mbar, preferably at least 1 *10 "4 mbar.
  • the pressure may be increased up to an order of magnitude of 10 "2 mbar.
  • the metal to be evaporated is Ti and the pressure in the chamber is increased by means of Ar.
  • the pressure in the chamber should be at least 5 * 10 '5 mbar, preferably at least 1 * 10 '4 mbar. It could also be increased up to an order of magnitude of 10 '2 mbar.
  • the substrate is provided with several coating layers by the method indicated above, as shown in Figure 2.
  • the pressure while coating each layer may be the same or different.
  • By using different pressure for each coating layer it is possible to achieve a density gradient in the coating, for example a dense layer at the steel surface and a porous layer at the opposite side of the coating.
  • the increasing density of the coating is indicated by the arrow D.
  • the produced coated steel strip is suitable for use in laminated structures, especially metallic laminated structures or fiber metal laminates.
  • This is illustrated in Figure 3, showing two coated substrates 3 and one uncoated substrate 4.
  • the coated substrates 3 and the uncoated substrates 4 are joined by an adhesive 6, such as a polymer based adhesive.
  • the different substrates applied to the substrates in this embodiment may be of the same or of different compositions.
  • coated substrate 3 may be a stainless steel substrate provided with a Ti comprising coating and the uncoated substrate 4 may be of a Ni alloy.
  • Metallic laminates or fiber metal laminates may for example be used as constructional parts or body sheets for vehicles such as cars, busses, trucks, ship and aircrafts.
  • One example of a suitable application is in laminates comprising at least two metal sheets, for example of steel, between which there are provided threads or fibers and wherein the metal sheets and the threads/fibers are bonded together by means of an adhesive.
  • Such a laminate is for example disclosed in US 4 489 123 and may be used in aircraft or space applications.
  • the produced coated steel strip is suitable for constructional parts which should be painted/lacquered or otherwise surface treated and requiring high adherence of the painted coating to the substrate.
  • This embodiment is illustrated in Figure 4, showing a coated substrate 3 having an additional coating layer of a lacquer 5.
  • the coated substrate may be used in many applications. Especially, it can be utilized in metallic laminates or FML used in armor applications.
  • One example of yet another type of laminate is shown in Figure 5 wherein a coated substrate 3 produced in accordance with the present invention is attached to a corrugated laminate layer 7 or a honeycomb shaped layer (not shown).
  • the corrugated laminate layer may be attached to further coated substrates produced in accordance with the present invention as shown in the figure.
  • This type of laminates is illustrated in US 5 874 153.
  • the substrate is a wire which should be used to manufacture a metallic web; the coated wire provides high adherence to an adjacent coated wire by means of an adhesive provided to the contact point.
  • the method according to the present disclosure may also be used to produce components for biomedical applications, such as prostheses or implants.
  • a porous coating in accordance with the present invention may provide a good bond to bone tissue and substantially reduce wear of a metal substrate.
  • Ti and Co based alloys are furthermore well known for their biocompatible properties.
  • the wetting properties was determined by measuring the contact angle with the surface of the samples of drops of three different liquids, distilled water (H 2 O), ethylene glycol (hereafter also denoted EG) and diiodine methane (CH 2 I 2 ). Before testing, the samples were cleaned with pure ethanol in order to remove impurities and possible fingerprints. Table 1
  • the measurements were conducted by means of Fibro DAT 1100 (dynamic absorption tests) by dropping drops of liquid from a height of 10 mm above the surface of the sample.
  • the volumes of the drops were 4 ⁇ l for water and ethylene glycol, and 1 ,8 ⁇ l for diiodine methane.
  • the drop was filmed from the side using a CCD camera. It was noted that after 10-20 seconds the contact angles of the drops were stabilized and reached equilibrium. Unfortunately, contact angles less than 15° are outside the measuring range of the instrument used, whereby the exact equilibrium of these could not be determined. In four cases the contact angles was observed to be considerably less than 15°, therefore these were set to ⁇ 10°.
  • Table 2 The results are listed in Table 2 and illustrated in Figure 6.
  • the surface energy ysv- The basis is that the interaction between a liquid and a solid surface is dominated by van der Waals (hereafter denoted vdW) and acid-base interactions, respectively.
  • vdW van der Waals
  • the surface energy ysv can be calculated by the contribution of a polar component / s and a dispersive component ⁇ vdW , as illustrated in Equation 1.
  • the contact angle is denoted ⁇ ; and L, S, V stand for liquid, solid and vapor, respectively.
  • Example 3 Depending on the gas used for the pressure regulation of the evaporation process different coating morphologies were obtained. If comparing the samples given in Example 3, i.e. samples 5-8, with the samples from Example 4 i.e. the samples 9-12, it can clearly be seen that the utilization of the embodiment with Ar gives sub-micrometer sized gains which are larger than the grains produced using nitrogen as the regulating gas. This increased grain size will lead to an even rougher surface than the embodiment with N 2 . Furthermore, the randomly oriented flake like grains of the Ar gas regulated coatings has a grain size of approximately 150 nm while the more triangular shape grains for the nitrogen gas regulated coating has a grain size of approximately 50 nm.

Abstract

L'invention concerne un procédé de production de substrats métalliques présentant une surface adhésive. Un revêtement est appliqué sur le substrat par évaporation par faisceau électronique. La pression du gaz dans la chambre de revêtement est augmentée comparée à la pression de revêtement normale.
PCT/SE2006/000894 2006-07-19 2006-07-19 Procédé de production d'une surface rugueuse sur un substrat WO2008010747A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/SE2006/000894 WO2008010747A1 (fr) 2006-07-19 2006-07-19 Procédé de production d'une surface rugueuse sur un substrat

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/SE2006/000894 WO2008010747A1 (fr) 2006-07-19 2006-07-19 Procédé de production d'une surface rugueuse sur un substrat

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WO2008010747A1 true WO2008010747A1 (fr) 2008-01-24

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344316A1 (fr) * 1987-07-30 1989-12-06 Matsushita Electric Industrial Co., Ltd. Procede de fabrication d'un condensateur electrolytique
US4963151A (en) * 1988-12-28 1990-10-16 Trustees Of The University Of Pennsylvania Reinforced bone cement, method of production thereof and reinforcing fiber bundles therefor
JPH05311444A (ja) * 1992-05-08 1993-11-22 Citizen Watch Co Ltd 硬質カーボン膜の構造
JPH06199068A (ja) * 1993-01-08 1994-07-19 Nippon Steel Corp 親水性セラミックス被覆ローラ
GB2282389A (en) * 1990-03-02 1995-04-05 Minnesota Mining & Mfg Coated fibers
EP0685439A2 (fr) * 1994-05-30 1995-12-06 Ebara Corporation Joint d'étachéité ou palier
EP0905274A1 (fr) * 1996-04-03 1999-03-31 Zakrytoe Aktsionernoe Obschestvo "Ross Ltd" Procede et dispositif de deposition de revetement poreux et feuille cathodique de condensateur electrolytique
JP2005314766A (ja) * 2004-04-30 2005-11-10 ▲ほん▼暉實業股▲ふん▼有限公司 金属製品の製造方法及びその製品

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0344316A1 (fr) * 1987-07-30 1989-12-06 Matsushita Electric Industrial Co., Ltd. Procede de fabrication d'un condensateur electrolytique
US4963151A (en) * 1988-12-28 1990-10-16 Trustees Of The University Of Pennsylvania Reinforced bone cement, method of production thereof and reinforcing fiber bundles therefor
GB2282389A (en) * 1990-03-02 1995-04-05 Minnesota Mining & Mfg Coated fibers
JPH05311444A (ja) * 1992-05-08 1993-11-22 Citizen Watch Co Ltd 硬質カーボン膜の構造
JPH06199068A (ja) * 1993-01-08 1994-07-19 Nippon Steel Corp 親水性セラミックス被覆ローラ
EP0685439A2 (fr) * 1994-05-30 1995-12-06 Ebara Corporation Joint d'étachéité ou palier
EP0905274A1 (fr) * 1996-04-03 1999-03-31 Zakrytoe Aktsionernoe Obschestvo "Ross Ltd" Procede et dispositif de deposition de revetement poreux et feuille cathodique de condensateur electrolytique
JP2005314766A (ja) * 2004-04-30 2005-11-10 ▲ほん▼暉實業股▲ふん▼有限公司 金属製品の製造方法及びその製品

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199401, Derwent World Patents Index; AN 1994-002427, XP002423931 *
DATABASE WPI Week 199433, Derwent World Patents Index; AN 1994-269194, XP002423930 *

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