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EP3978191A1 - Modification de surfaces par projection abrasive - Google Patents

Modification de surfaces par projection abrasive Download PDF

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Publication number
EP3978191A1
EP3978191A1 EP21208806.6A EP21208806A EP3978191A1 EP 3978191 A1 EP3978191 A1 EP 3978191A1 EP 21208806 A EP21208806 A EP 21208806A EP 3978191 A1 EP3978191 A1 EP 3978191A1
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EP
European Patent Office
Prior art keywords
abrasive
dopant
particles
microns
metal
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EP21208806.6A
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German (de)
English (en)
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EP3978191B1 (fr
Inventor
Barry TWOMEY
John O'donoghue
Kevin Roche
Liam O'neill
Paolo Vincenzo Ercole FIORINI
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EnBIO Ltd
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EnBIO Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C11/00—Selection of abrasive materials or additives for abrasive blasts
    • B24C11/005—Selection of abrasive materials or additives for abrasive blasts of additives, e.g. anti-corrosive or disinfecting agents in solid, liquid or gaseous form
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles

Definitions

  • the present invention relates to surface treatment techniques in the field of materials science.
  • Metal surface finish is often provided using particle bombardment. This can vary from material removal using abrasive blasting through to material deposition using cold spraying. The difference in these approaches rests in the energy of the processes.
  • the cold spray process actually uses elevated temperatures.
  • the gas used to carry the particles is heated to a temperature of several hundred degrees, typically between 200°C and 1000°C, before it is mixed with the bombardment particles. This increases the gas velocity without increasing the line pressure feeding the gas.
  • cold spray processes operate at elevated temperatures but below the melting point of the metallic bombardment particles that are employed.
  • the kinetic energy of the bombarding particles is also higher in cold spray systems as the particles travel at significantly higher velocities than in abrasive blasting.
  • the particles are typically accelerated to supersonic speeds (greater than 342 m/sec). At high velocities, greater than 300 m/sec, the energy imparted by the impact of the particle against the surface can be sufficient to cause both the metal surface and the bombarding metal particle to deform and the resultant interaction causes the particle to spread out and coat the surface.
  • the minimum velocity required to achieve this coating deposition is referred to as the 'critical velocity' in cold spray technology. Due to the requirement for the bombarding particle to deform upon impact, there has been limited applicability of this technology to the deposition of non-metallic materials. At values below the critical velocity, very little impregnation of the surface occurs and the bombarding particles typically bounce off the surface.
  • the widely quoted minimum critical velocity for a wide range of materials is 400 m/sec, as outlined in Grigoriev et al. (Surf. Coat. Technol., 268 (2015), pg 77-84 ) and as shown in the present Figure 1 , which is taken from that publication. This value can vary depending upon the bombarding particles and the properties of the substrate surface.
  • an oxide layer forms at the surface, which will be harder than the bulk metal or alloy.
  • Metal surfaces especially those of titanium and titanium derived alloy
  • the detailed physical and chemical properties of any metal surface depend on the conditions under which they are formed.
  • the inherent reactivity of the metal can also attract various environmental chemicals/contaminants that oxidize on the surface.
  • titanium is a highly reactive metal, which is readily oxidized by several different media. This results in titanium, and most other metals, always being covered in an oxide layer.
  • This oxide layer is chemically stable and much harder than the bulk metal underneath.
  • the ability of the bombarding particles to bond to the substrate is often limited by the properties of the oxide and not by the properties of the underlying metal.
  • cold spray technologies which are also limited by the properties of the surface that can be treated.
  • the substrate surface In order for the cold spray coating to adhere, the substrate surface must be cleaned and roughened. This is often accomplished by abrasively blasting the surface before cold spraying.
  • cold spray coatings have been undertaken which also incorporate some abrasive particles alongside the metal dopant, but these have all been deposited at high velocities and at elevated temperatures beyond the range of abrasive blasting.
  • the presence of the ceramic particles acts to increase the deposition rate of the metal.
  • the presence of the ceramic may enhance the wear resistance of the deposit.
  • the edges and corners of the bombarding particles can cut up and erode material from the substrate metal. This results in abrasion of the surface, and abrasive blasting is widely used to clean and roughen metal surfaces.
  • the abrasive particles are chosen to have a Mohs hardness of at least 5, though harder particles are preferred as the abrasion increases with hardness.
  • each particle comprises a vitreous crystalline material made from a combination of CaO, P 2 O 5 , ZrO 2 and fluoride.
  • the resultant particles are embedded in the surface to improve the biocompatibility of the metal surface.
  • US 3,754,976 describes a process for metal plating. While cold spray uses high velocity bombardment to adhere a metal to a surface, this patent disclosed a process for metal plating in which a mixture of metallic powder and small shot peening particles are sprayed against a surface at a velocity sufficient to impact and bond the metallic powder onto the surface. The peening particles effectively deform and plate the metal particles onto the surface without any significant uptake of peening particles in the coating. This technique was later expanded to include additional materials that could be deposited. US 4,552,784 describes a process for depositing rapidly solidified metal powder using this technique.
  • US 4,753,094 claims a process wherein a combination of molybdenum disulphide and round metal shot was blasted at a surface to deposit a layer of molybdenum disulphide.
  • US 2006/0089270 claims a process wherein shot peening particles are mixed with a primary lubricant such as molybdenum disulphide and a polymeric lubricant such as polytetrafluoroethylene (PTFE) and blasted at a surface to deposit a mixture of the two lubricants on the surface.
  • PTFE polytetrafluoroethylene
  • a metal surface treatment method wherein the surface is simultaneously bombarded with a mixture of abrasive particles and dopant particles which are delivered at a velocity in the range of 50-250 m/sec (metres per second), and thereby depositing the dopant material on the surface.
  • the particles may be delivered at a velocity in the range of 100-200 m/sec, for example at a velocity in the range of 120-180 m/sec.
  • the method may be carried out at ambient temperature.
  • the abrasive particles have an irregular or angular morphology.
  • the dopant may be directly chemically bonded to the metal surface without any intermediate oxide layer.
  • the dopant particles may be agglomerated together on the metal surface.
  • the abrasive has a hardness greater than 6.0 on the Mohs scale.
  • the abrasive may have a hardness of 8.0 or above on the Mohs scale.
  • the abrasive has a hardness at least 2 levels higher than that of the dopant on the Mohs scale.
  • the abrasive has a hardness at least 3 levels higher than that of the dopant on the Mohs scale.
  • the dopant may be a polymer or other low density material (having a density of less than 2.5 g/cm 3 ) and the abrasive may have an average particle size in the range of 150-1500 microns ( ⁇ m).
  • the abrasive may have an average particle size in the range of 250-1000 microns, such as in the range of 350-750 microns.
  • the abrasive may have an average particle size of greater than 300 microns.
  • the dopant may be a polymer (or alternatively may be a non-polymer), and the abrasive may have an average particle size in the range of 5-5000 microns, such as in the range of 5-1500 microns.
  • the dopant may be a polymer and the abrasive may have an average particle size in the range of 10-150 microns.
  • the variation in abrasive size is typically associated with the desired texture required on the finished surface.
  • the abrasive may constitute at least 60wt% of the mixture of abrasive and dopant particles.
  • the abrasive constitutes at least 70wt% of the mixture of abrasive and dopant particles. More preferably the abrasive constitutes at least 80wt% of the mixture of abrasive and dopant particles.
  • the dopant may be a non-polymeric material and the abrasive may have an average particle size of less than 500 microns.
  • the abrasive may have an average particle size of less than 200 microns, or less than 150 microns.
  • the dopant may constitute at least 20wt% of the mixture of abrasive and dopant particles.
  • the dopant constitutes at least 25wt% of the mixture of abrasive and dopant particles. More preferably the dopant constitutes at least 40wt% of the mixture of abrasive and dopant particles.
  • the dopant particles may have an average particle size in the range of 1-100 microns.
  • dopant material typically less than 10 microns are deposited on the surface.
  • At least some of the dopant particles may penetrate the metal surface and remain physically impregnated in the metal.
  • one or more additional coatings may subsequently be applied on top of the deposited dopant material.
  • an additional coating may be applied through a bombardment technique selected from cold spray, peen plating or microblasting. Other ways of applying an additional coating are also possible, such as powder coating or painting.
  • the surface that is treated may be at least a part of:
  • WO 2008/033867 describes techniques for the substantially simultaneous deposition of first and second sets of particles.
  • first and second sets of particles are different from one another. That is to say, the dopant species is different from the abrasive.
  • Embodiments of the CoBlast method are encompassed in but not limited to the schematic representation shown in Figures 2a, 2b and 2c .
  • Figure 2a schematically shows a fluid jet (nozzle) 2 that delivers a stream 3 comprising a set of abrasive particles 4 substantially simultaneously with a set of dopant particles 6.
  • Particle sets 4 and 6 bombard a surface 10 of a metal substrate 8, to impregnate the surface of the metal substrate with the dopant.
  • the surface 10 is a metal oxide layer.
  • the surface oxide layer is disrupted, and breaches in the oxide layer 10 result to expose a new surface 10a of substrate 8 ( Figure 2b ).
  • the newly exposed surface is a metal surface.
  • the dopant particles 6 are integrated into the surface 10 of the substrate 8 ( Figure 2c ).
  • the blasting equipment can be used in conjunction with controlled motion such as CNC (computer numerical control) or robotic control. Either the blast nozzle, the substrate or both may be manipulated so as to achieve the desired surface treatment.
  • the blasting can be performed in an inert environment.
  • the use of an inert atmosphere is typically required to manage explosion or flammability risks associated with dopant or substrate materials and is not a specific requirement in forming a coating.
  • the dopant and abrasive particles are contained in the same reservoir and are delivered to a surface from the same jet (nozzle).
  • the dopant particles are contained in one reservoir and the abrasive particles are contained in a separate reservoir, and multiple nozzles deliver the dopant and abrasive particles.
  • the multiple nozzles can take the form of a jet within a jet, i.e., the particles from each jet bombard the surface at the same incident angle.
  • the multiple nozzles are spatially separated so as to bombard the surface at different incident angles yet hit the same spot on the surface simultaneously.
  • Figures 3a, 3b and 3c are schematic diagrams of three different nozzle configurations to deliver the dopant and abrasive particles to a surface: single nozzle ( Figure 3a ); multiple nozzles with dopant and abrasive particles delivered from separate reservoirs where one nozzle is situated within another nozzle ( Figure 3b ); and multiple, separate nozzles with dopant and abrasive particles delivered from separate reservoirs ( Figure 3c ). More specifically, Figure 3a shows a single nozzle 20 for delivering a single stream 23 of abrasive particles 24 and dopant particles 26 to a substrate 28.
  • Figure 3b shows that multiple nozzles with dopant and abrasive particles delivered from separate reservoirs can be used, with Figure 3b illustrating one nozzle 30 for delivering a stream 33 of abrasive particles 24 situated within another nozzle 40 for delivering a stream 43 of dopant particles 26, where streams 33 and 43 are coaxial.
  • Multiple, separate nozzles with dopant and abrasive particles delivered from separate reservoirs can also be used, as indicated in Figure 3c , which shows nozzles 30 and 40, for delivering streams 33 and 43 of abrasive particles 24 and dopant particles 26, respectively.
  • the distance D between the nozzle(s) and the substrate surface can be in the range of 0.1 mm to 250 mm, such as a range of 0.1 mm to 130 mm, or a range of 5 mm to 50mm.
  • the angle of the nozzle to the surface can range from 10 degrees to 90 degrees, such as a range of 30 degrees to 90 degrees, or a range of 70 to 90 degrees.
  • dopant species More than one type of dopant species can be used. It will readily be appreciated that where more than one type of dopant is used, the dopants may be delivered from a single nozzle, or each type may respectively be delivered from a separate nozzle.
  • More than one type or size of abrasive can be used. This may be undertaken to both assist in the deposition of dopant material and also to customise the surface topography and level of texturing during processing. It will readily be appreciated that where more than one type of abrasive is used, the abrasives may be delivered from a single nozzle, or each type may respectively be delivered from a separate nozzle.
  • an optimised coating can result from premixing an angular abrasive with a particulate dopant, and delivering the powder mix to a metal substrate surface at a velocity of 50-250 m/sec, so as to remove the oxide layer from the surface, and simultaneously depositing less than 10 microns of dopant on the surface. At least a portion of the deposited materials penetrate the metal surface and remain impregnated within the metal. This process also results in direct chemical bonding of the dopant to the surface, without the presence of any intermediate oxide layer.
  • the mixture of abrasive and dopant particles is delivered at a velocity of 100-200 m/sec to the surface.
  • the particles are delivered at a velocity of 120-180 m/sec. If the dopant particles are delivered at a different velocity than the abrasive particles, then it has been found that the velocity of the abrasive particles dominates the effect at the surface, and therefore it is the abrasive that has to be delivered at the correct velocity.
  • an angular abrasive particle with a hardness greater than 6.0 on the Mohs scale is required.
  • a harder abrasive can increase the deposition rate and an abrasive with a hardness of 8.0 or above is preferred.
  • an abrasive such as this is sufficient to remove the oxide layer from a metal even at low velocity.
  • the abrasive cleans the surface and ensures that no complex cleaning or roughening of the surface is needed prior to deposition.
  • the abrasive removes the oxide and also erodes some of the metal underneath.
  • the impact of the abrasive also acts to roughen and twist the metal surface, thereby embedding and interlocking the dopant into the surface.
  • the Mohs hardness of the abrasive is preferably chosen to be at least 2 levels higher than that of the dopant. This ensures preferential uptake of the dopant and minimal impregnation of the abrasive into the surface.
  • the abrasive is at least 3 levels harder than the dopant on the Mohs scale.
  • the dopant is found to be chemically bonded to the surface. Given that the reaction happens in ambient atmosphere, it is surprising that there is no evidence of oxide layers between the dopant and the metal. Instead, the dopant is bonded directly to the reactive metal. This ensures excellent adhesion of the dopant to the metal.
  • the dopant particles are shattered and torn by the impact on the surface and the ongoing abrasive action of the abrasive particle bombardment. For crystalline or semi-crystalline dopant powders, this can produce nano-crystalline dopant particles on the surface, and the resultant high surface energy and reactivity of these sub-micron particles results in materials that bond readily with the metal and which also agglomerate and fuse together on the surface.
  • the process can occur at ambient temperature and neither the substrate nor the gas stream need be heated as in cold spray. All of the reactions occur at less than 100°C. Although there is no direct heating and it is a room temperature process, the localised heating induced by the kinetic energy of the impact of the particles may be important in localised reactions. For example, during the deposition of polymeric dopants, the localised reactions may give rise to T G modification of the polymer material.
  • the bombardment of the surface does alter the structure of the substrate.
  • microscopic analysis has shown that the abrasive alters the structure of the metal substrate, switching it from coarse grains to fine grains, thereby making it more reactive.
  • the formation of nano-crystallinity also occurs on the substrate side of the interface.
  • Blasting induces a level of Severe Plastic Deformation (SPD) on the substrate and the bombardment thereby increases the dislocation density at the newly exposed surface, which increases the numbers of ultra-fine grains and therefore the overall density of grain boundaries. Grain boundaries provide reaction sites and thus increase the reactivity of a surface.
  • SPD Severe Plastic Deformation
  • This increase in grain boundary availability increases the reactivity of the metal interface to a depth of 20 ⁇ m.
  • this work hardening of the metal could also be expected to enhance the bonding of the dopant to the substrate.
  • there is no heat affected zone as would be expected from a high energy plasma spray or hot deposition process.
  • This combination of effects gives rise to direct chemical bonding of the dopant to the substrate. In the case of ceramic dopants, this can give rise to a diffusion bonded material.
  • the work hardening also improves the fatigue life of the metal substrate when compared to untreated components.
  • the localised reactions also allow for materials to be deposited in an adherent manner which do not normally stick.
  • materials such as PTFE are routinely used as non-stick surfaces as it is notoriously difficult to make PTFE adhere to anything.
  • the abrasive actually shreds the polymer chain and leaves dangling, unreacted chemical bonds where the chain was cut. Those would provide very reactive sites that could bind to reactive sites on the metal surface and thereby facilitate chemical bonding of the PTFE to the substrate.
  • polymeric materials such as PTFE are stable and quite non-reactive, additional energy may be required to induce the reactions that bond the material to the surface. Therefore, when depositing polymeric materials, it may be beneficial to use higher velocity deposition parameters. However, higher velocities require higher gas flows and therefore it is instead preferred to use a larger size abrasive grit to provide additional kinetic energy. If abrasive particles greater than 1500 microns in size are used, then there are insufficient impacts per unit area to bond the polymer to the surface. If small grit particles less than 150 microns in size are used, then the impinging abrasive may lack the kinetic energy to induce reactions with the non-reactive polymer material.
  • abrasive particles of 150 to 1500 microns in size preferably 250 to 1000 microns in size, and most preferably 350 to 750 microns in size as these possess higher kinetic energy and produce enhanced surface abrasion and roughening.
  • abrasive particles having an average particle size of the order of 50 microns or smaller and, separately, using abrasive particles having an average particle size of the order of 13 microns or smaller.
  • the blend of dopant and abrasive should be altered to be rich in abrasive. While standard blasting is carried out with equal mixtures by weight of dopant and abrasive, for polymer dopants it has been found that a ratio of at least 60wt% abrasive and a maximum of 40wt% dopant is preferred. A more preferred ratio comprises at least 70wt% abrasive and no more than 30wt% dopant. In the most preferred ratio, the mixture comprises 80-90wt% abrasive and 10-20wt% dopant.
  • dopant materials can be achieved using abrasives with an average particle size of 500-1000 microns, it has been observed that better results occur with abrasive particles that are less than 500 microns, preferably less than 200 microns, and ideally in the range of 10-150 microns average particle size.
  • the maximum ratio of abrasive to dopant has been found to be 80wt% abrasive to 20wt% dopant, with better loading of the dopant formed when the mixture contains no more than 75wt% abrasive and at least 25wt% dopant.
  • the optimum surface loading of non-polymeric dopants is achieved when the mixture contains no more than 60wt% abrasive and greater than 40wt% dopant. Although a range of abrasive particles have been successfully employed in CoBlast, the average dopant particle is typically in the range of 1-100 microns in size.
  • a blend of abrasive sizes may also be used when depositing dopant particles using the CoBlast process.
  • large abrasive particles may be used for surface profile and cleaning effects, simultaneously with small abrasive particles in order to achieve good surface coverage and improved reactivity.
  • abrasive particles e.g. having an average particle size of the order of 1500 microns or greater
  • CoBlast process using small abrasive particles simultaneously with the dopant particles
  • the optimal coating may be produced using smaller particles, but the requirement to flow the particles in a smooth and continuous manner from one or more hoppers to the/each delivery nozzle may require the addition of flow agents or the use of larger abrasive or dopant particles.
  • the mixture of abrasive and dopant should have a Hausner ratio of less than 1.2 (and particularly preferably less than 1.15).
  • the hopper should be loaded with no more than 400g of mixed media. In order to ensure a constant supply to the nozzle, it may be beneficial to employ multiple powder feeders each loaded with small quantities of mixed media, preferably less than 500g.
  • Hausner ratio values in the above paragraph are by way of example only, in respect of a specific deposition system we use. For other configurations of the apparatus the Hausner ratio values may differ.
  • the deposited CoBlast layer is typically limited to a thin deposit of 2-5 microns, although thicker deposits of up to 10 microns are possible. When attempting to produce thicker deposits, the presence of the abrasive eventually begins to produce excess abrasion and thicker coatings are rapidly removed, meaning that the process is self-limiting with a maximum thickness of 10 microns achievable. In order to deposit thicker coatings, it is beneficial to first deposit a CoBlast layer using a combination of dopant and abrasive. This produces a thin and chemically bonded primer layer onto which additional materials can then be deposited. In a preferred embodiment, the CoBlast process is used to deposit a thin layer of dopant on the surface.
  • the flow of abrasive and dopant is then switched off or redirected and a second bombardment of the surface takes place.
  • This second bombardment can be based on a cold spray process in which additional materials are blasted at the surface with the required critical velocity to adhere the particles to the surface.
  • the benefit of first employing the CoBlast process is that this facilitates the direct chemical bonding of the coating to the metal without an intervening oxide layer and thereby minimises the risk of coating delamination.
  • the second bombardment may be carried out using a mixture of dopant particles and round shot peen particles.
  • the switch from angular abrasive grit to spherical shot peen particles ensures that the secondary process is not dominated by abrasive erosion, and thick coatings can be grown which are anchored to the metal surface by the CoBlast primer layer.
  • This secondary bombardment can be carried out using the same equipment as used in the CoBlast treatment or can comprise a second set of equipment.
  • the secondary bombardment may involve simply blasting a dopant, without any additional material, at the CoBlast treated surface so as to build up a thicker coating, but without using the high temperatures or high velocity of the cold spray process. This represents a microblast process similar to that described by Ishikawa.
  • the dopant used in any of the secondary bombardment steps may be identical to the dopant used in the CoBlast treatment or it may be different from the CoBlast dopant materials.
  • the CoBlast layer will act to improve adhesion of the secondary coating by directly bonding the top coat to the metal without any oxide interface.
  • the top coating is then further processed using thermal, laser, e-beam or some other high energy method in order to cross-link, melt, densify or cure the coating. This also causes the top layer to fuse with the CoBlast primer layer, thereby chemically bonding the top coat directly to the metal substrate.
  • the secondary surface treatment may be added using traditional methods such as painting, sputtering, CVD, plasma deposition, ion plating, PVD, ion beam assisted deposition, electron beam PVD, cathodic arc deposition, magnetron sputtering, vacuum evaporation, laser assisted deposition, PECVD, electroplating, spraying, HVOF, powder coating, dip coating, inkjet printing, roller coating, lithography, spin coating or other such technologies.
  • the initial layer of dopant acts as a primer that allows the top coating to be bound directly to the metal substrate without any intermediate oxide layer. Further curing or heating of the top coat can enhance the bonding to the substrate further.
  • the dopant can comprise materials such as polymers, metals, ceramics (e.g., metal oxides, metal nitrides), and combinations thereof, e.g., blends of two or more thereof.
  • Exemplary dopants include modified calcium phosphates, including Ca 5 (PO 4 ) 3 OH, CaHPO 4 ⁇ 2H 2 O, CaHPO 4 , Ca 8 H 2 (PO 4 ) 6 ⁇ 5H 2 O, ⁇ -Ca 3 (PO 4 ) 2 , ⁇ -Ca 3 (PO 4 ) 2 , tetracalcium phosphate, beta calcium phosphate or any modified calcium phosphate containing carbonate, chloride, fluoride, silicate or aluminate anions, protons, potassium, sodium, magnesium, barium or strontium cations.
  • modified calcium phosphates including Ca 5 (PO 4 ) 3 OH, CaHPO 4 ⁇ 2H 2 O, CaHPO 4 , Ca 8 H 2 (PO 4 ) 6 ⁇ 5H 2 O, ⁇ -Ca 3 (PO 4 ) 2 , ⁇ -Ca 3 (PO 4 ) 2 , tetracalcium phosphate, beta calcium phosphate or any modified calcium phosphat
  • dopants include titania (TiO 2 ), hydroxyapatite, silica, calcium carbonate, biocompatible glass, calcium phosphate glass, carbon, graphite, graphene, chitosan, chitin, barium titanate, zeolites (aluminosilicates), including siliceacous zeolite and zeolites containing at least one component selected from phosphorous, silica, alumina, zirconia.
  • titania TiO 2
  • hydroxyapatite silica
  • silica calcium carbonate
  • biocompatible glass calcium phosphate glass
  • carbon graphite, graphene, chitosan, chitin
  • barium titanate zeolites (aluminosilicates)
  • zeolites aluminosilicates
  • the dopant is a therapeutic agent.
  • the therapeutic agent can be delivered as a particle itself, or immobilized on a carrier material.
  • exemplary carrier materials include any of the other dopants listed herein (those dopants that are not a therapeutic agent) such as polymers, calcium phosphate, titanium dioxide, silica, biopolymers, biocompatible glasses, zeolite, demineralized bone, de-proteinated bone, allograft bone, and composite combinations thereof.
  • Exemplary classes of therapeutic agents include anti-cancer drugs, anti-inflammatory drugs, immunosuppressants, an antibiotic, heparin, a functional protein, a regulatory protein, structural proteins, oligo-peptides, antigenic peptides, nucleic acids, immunogens, and combinations thereof.
  • the therapeutic agent is chosen from antithrombotics, anticoagulants, antiplatelet agents, thrombolytics, antiproliferatives, antiinflammatories, antimitotic, antimicrobial, agents that inhibit restenosis, smooth muscle cell inhibitors, antibiotics, fibrinolytic, immunosuppressive, and anti-antigenic agents.
  • anticancer drugs include acivicin, aclarubicin, acodazole, acronycine, adozelesin, alanosine, aldesleukin, allopurinol sodium, altretamine, aminoglutethimide, amonafide, ampligen, amsacrine, androgens, anguidine, aphidicolin glycinate, asaley, asparaginase, 5-azacitidine, azathioprine, Bacillus calmette-guerin (BCG), Baker's Antifol (soluble), beta-2'-deoxythioguanosine, bisantrene HCI, bleomycin sulfate, busulfan, buthionine sulfoximine, BWA 773U82, BW 502U83.HCl, BW 7U85 mesylate, ceracemide, carbetimer, carboplatin, carmustine, chlorambucil, chloroquinoxa
  • Exemplary therapeutic agents include immunogens such as a viral antigen, a bacterial antigen, a fungal antigen, a parasitic antigen, tumor antigens, a peptide fragment of a tumor antigen, meta static specific antigens, a passive or active vaccine, a synthetic vaccine or a subunit vaccine.
  • the dopant may be a protein such as an enzyme, antigen, growth factor, hormone, cytokine or cell surface protein.
  • the dopant may be a pharmaceutical compound such as an anti-neoplastic agent, an anti-bacterial agent, an anti-parasitic agent, an anti-fungal agent, an analgesic agent, an anti-inflammatory agent, a chemotherapeutic agent, an antibiotic or combinations thereof.
  • a pharmaceutical compound such as an anti-neoplastic agent, an anti-bacterial agent, an anti-parasitic agent, an anti-fungal agent, an analgesic agent, an anti-inflammatory agent, a chemotherapeutic agent, an antibiotic or combinations thereof.
  • the dopant could also be growth factors, hormones, immunogens, proteins or pharmaceutical compounds that are part of a drug delivery system such as those immobilized on zeolite or polymeric matrices, biocompatible glass or natural porous apitic templates such as coralline HA, demineralised bone, deproteinated bone, allograft bone, collagen or chitin.
  • the dopant is an anti-inflammatory drug selected from non-steroidal anti-inflammatory drugs, COX-2 inhibitors, glucocorticoids, and mixtures thereof.
  • non-steroidal anti-inflammatory drugs include aspirin, diclofenac, indomethacin, sulindac, ketoprofen, flurbiprofen, ibuprofen, naproxen, piroxicam, tenoxicam, tolmetin, ketorolac, oxaprosin, mefenamic acid, fenoprofen, nambumetone, acetaminophen, and mixtures thereof.
  • COX-2 inhibitors include nimesulide, NS-398, flosulid, L-745337, celecoxib, rofecoxib, SC-57666, DuP-697, parecoxib sodium, JTE-522, valdecoxib, SC-58125, etoricoxib, RS-57067, L-748780, L-761066, APHS, etodolac, meloxicam, S-2474, and mixtures thereof.
  • Exemplary glucocorticoids include hydrocortisone, cortisone, prednisone, prednisolone, methylprednisolone, meprednisone, triamcinolone, paramethasone, fluprednisolone, betamethasone, dexamethasone, fludrocortisone, desoxycorticosterone, and mixtures thereof.
  • exemplary therapeutic agents include cell cycle inhibitors in general, apoptosis-inducing agents, antiproliferative/antimitotic agents including natural products such as vinca alkaloids (e.g., vinblastine, vincristine, and vinorelbine), paclitaxel, colchicine, epidipodophyllotoxins (e.g., etoposide, teniposide), enzymes (e.g., L-asparaginase, which systemically metabolizes L-asparagine and deprives cells that do not have the capacity to synthesize their own asparagine); antiplatelet agents such as G(GP) IIb/IIIa inhibitors, GP-IIa inhibitors and vitronectin receptor antagonists; antiproliferative/antimitotic alkylating agents such as nitrogen mustards (mechlorethamine, cyclophosphamide and analogs, melphalan, chlorambucil), ethylenimines and methylmelamine
  • the dopant is an antibiotic chosen from tobramycin, vancomycin, gentamicin, ampicillin, penicillin, cephalosporin C, cephalexin, cefaclor, cefamandole and ciprofloxacin, dactinomycin, actinomycin D, daunorubicin, doxorubicin, idarubicin, penicillins, cephalosporins, and quinolones, anthracyclines, mitoxantrone, bleomycins, plicamycin (mithramycin), mitomycin, polyketide antibiotics such as tetracycline, and mixtures thereof.
  • an antibiotic chosen from tobramycin, vancomycin, gentamicin, ampicillin, penicillin, cephalosporin C, cephalexin, cefaclor, cefamandole and ciprofloxacin, dactinomycin, actinomycin D, daunorubicin, doxorubicin,
  • the dopant is a protein chosen from albumin, casein, gelatin, lysosime, fibronectin, fibrin, chitosan, polylysine, polyalanine, polycysteine, Bone Morphogenetic Protein (BMP), Epidermal Growth Factor (EGF), Fibroblast Growth Factor (bFGF), Nerve Growth Factor (NGF), Bone Derived Growth Factor (BDGF), Transforming Growth Factor-.beta.1 (TGF-.beta.1), Transforming Growth Factor-.beta.
  • BMP Bone Morphogenetic Protein
  • EGF Epidermal Growth Factor
  • bFGF Fibroblast Growth Factor
  • NGF Nerve Growth Factor
  • BDGF Bone Derived Growth Factor
  • TGF-.beta.1 Transforming Growth Factor-.beta.1
  • TGF-.beta. the tri-peptide arginine-glycine-aspartic acid (RGD), vitamin D3, dexamethasone, and human Growth Hormone (hGH), epidermal growth factors, transforming growth factor ⁇ , transforming growth factor ⁇ , vaccinia growth factors, fibroblast growth factors, insulin-like growth factors, platelet derived growth factors, cartilage derived growth factors, interlukin-2, nerve cell growth factors, hemopoietic cell growth factors, lymphocyte growth factors, bone morphogenic proteins, osteogenic factors, chondrogenic factors, and mixtures thereof.
  • hGH human Growth Hormone
  • the dopant is a heparin selected from recombinant heparin, heparin derivatives, and heparin analogues or combinations thereof.
  • the dopant is an oligo-peptide, such as a bactericidal oligo-peptide.
  • the dopant is an osteoconductive or osteointegrative agent.
  • the dopant is an immunosuppressant, such as cyclosporine, rapamycin and tacrolimus (FK-506), ZoMaxx, everolimus, etoposide, mitoxantrone, azathioprine, basiliximab, daclizumab, leflunomide, lymphocyte immune globulin, methotrexate, muromonab-CD3, mycophenolate, and thalidomide.
  • an immunosuppressant such as cyclosporine, rapamycin and tacrolimus (FK-506), ZoMaxx, everolimus, etoposide, mitoxantrone, azathioprine, basiliximab, daclizumab, leflunomide, lymphocyte immune globulin, methotrexate, muromonab-CD3, mycophenolate, and thalidomide.
  • the carrier material is a polymer such as polyurethanes, polyethylene terephthalate, PLLA-poly-glycolic acid (PGA) copolymer (PLGA), polycaprolactone, poly-(hydroxybutyrate/hydroxyvalerate) copolymer, poly(vinylpyrrolidone), polytetrafluoroethylene, poly(2-hydroxyethylmethacrylate), poly(etherurethane urea), silicones, acrylics, epoxides, polyesters, urethanes, sesnes, polyphosphazene polymers, fluoropolymers, polyamides, polyolefins, and blends and copolymers thereof.
  • polyurethanes polyethylene terephthalate
  • PGA PLLA-poly-glycolic acid copolymer
  • polycaprolactone poly-(hydroxybutyrate/hydroxyvalerate) copolymer
  • poly(vinylpyrrolidone) polytetrafluoro
  • the carrier material is a biopolymer selected from polysaccharides, gelatin, collagen, alginate, hyaluronic acid, alginic acid, carrageenan, chondroitin, pectin, chitosan, and derivatives, blends and copolymers thereof.
  • the dopant is a radio opaque material, such as those chosen from alkalis earth metals, transition metals, rare earth metals, and oxides, sulphates, phosphates, polymers and combinations thereof.
  • the dopant is a pigment designed to alter the emission, absorbance or reflectance of a surface.
  • the deposited pigment may comprise part of a thermal control surface.
  • the surface containing the deposited dopant may be electrically conductive. This conductivity may be sufficient to prevent the build-up of electrical static charge on the surface.
  • the dopant is a component present within an adhesive or paint. This component may bind to the adhesive or paint as it cures thereby chemically bonding the top layer to the substrate. Examples of such components include monomers, pre-polymers, pigments, silanes, fillers such as silica or clay .
  • the dopant may be fusion bonded epoxy, including of derivatives of bisphenol A and epichlorohydrin.
  • the dopant may be an epoxy prepolymer or may be derived from bisphenol A, bisphenol F, Novolac, Glycidylamine epoxy resins or aliphatic epoxy resin.
  • the component may be an additive such as accelerators, corrosion inhibitors, adhesion promoters, fire retardants or fungicides.
  • Typical corrosion-inhibiting dopant species that may be used in the present method include but are not limited to a chromate, phosphate, polymer, oxide or a nitride.
  • the dopant may be ceria.
  • the coating is derived from a phosphate compound.
  • the phosphate may comprise iron phosphate, manganese phosphate, zinc phosphate or combinations thereof.
  • a primer-forming dopant species may comprise a silane, siloxane, acrylate, epoxy, hydrogen bonded silicon compound or material which contains one or more vinyl, peroxyester, peroxide, acetate or carboxylate functional group.
  • Abrasive species that may be used in the present method include but are not limited to shot or grit made from silica, sand, alumina, zirconia, barium titanate, calcium titanate, sodium titanate, titanium oxide, glass, biocompatible glass, diamond, silicon carbide, boron carbide, dry ice, boron nitride, sintered calcium phosphate, calcium carbonate, metallic powders, carbon fibre composites, polymeric composites, titanium, stainless steel, hardened steel, carbon steel chromium alloys or any combination thereof.
  • the abrasive is chosen to be a different material than the dopant.
  • Exemplary metals include titanium, titanium alloys (e.g., NiTi or nitinol), ferrous alloys, stainless steel and stainless steel alloys, carbon steel, carbon steel alloys, aluminum, aluminum alloys, nickel, nickel alloys, nickel titanium alloys, tantalum, tantalum alloys, niobium, niobium alloys, chromium, chromium alloys, cobalt, cobalt alloys, magnesium and magnesium alloys, copper and copper alloys, precious metals, and precious metal alloys.
  • titanium alloys e.g., NiTi or nitinol
  • ferrous alloys e.g., NiTi or nitinol
  • stainless steel and stainless steel alloys e.g., carbon steel, carbon steel alloys, aluminum, aluminum alloys, nickel, nickel alloys, nickel titanium alloys, tantalum, tantalum alloys, niobium, niobium alloys, chromium, chromium alloys, cobal
  • the substrate is an implantable medical device.
  • implantable medical devices include catheters, guide wires, stents, dental implants, pulse generators, implantable orthopedic, spinal and maxillofacial devices, cochlear implant, needles, mechanical heart valves and baskets used in the removal of pathological calcifications.
  • biomedical devices it is desirable that the level of impregnation of the abrasive itself in the surface is minimal.
  • the abrasive should further be biocompatible as it is likely that some impregnation will occur.
  • the substrate is a vehicle component, including an automotive chassis, body or panel component, or an aerospace vehicle, satellite, rocket or spacecraft component, or a marine ship or boat component, specifically the outer hull.
  • the substrate is an engine or an engine component including exhaust outlets.
  • the substrate may be an electronic component, including components for use in applications in the Communication Infrastructure, Aerospace and Defense, Automotive, Mobile and Consumer Electronics, and High Speed Digital markets.
  • the electronic components may include circuit boards, cases, housing, switches, terminals, protection devices, transducers, capacitors, resistors, heat exchangers, antennas, human interfaces, dielectrics, thermal control surfaces, power sources or display components.
  • the substrate is a mould such as that used in the manufacture of plastic, silicone, rubber, composite, polymer, clay, glass, metal or ceramic materials.
  • the dopant may be chosen to enhance release of the cast part from the mould and the dopant may comprise a fluoropolymer or silicone material.
  • the substrate may be a pipe, tube or storage vessel, specifically one used in the petrochemical, marine, pharmaceutical, chemical, biotech or food and beverage industry.
  • the deposited dopant may be chosen to minimise fouling or build-up of materials on the inside of the container.
  • the dopant and abrasive are preferentially mixed together and blasted at a surface.
  • the blasting may be carried out using wheel abrading equipment or fluid based blast equipment.
  • the fluid may be a gas or a liquid, such as water.
  • Appropriate gases include air, nitrogen, argon, helium, carbon dioxide or mixtures thereof.
  • the fluid may comprise water or may be largely composed of an inert gas.
  • alumina abrasive 150 micron alumina abrasive was mixed with calcium phosphate (Hydroxyapatite or HA, 20-65 micron average particle size) and blasted at a series of grade 2 titanium coupons. The velocity of the bombarding particle was varied from 170-195 m/sec. Samples were then washed and examined using SEM. In each case, the surface was found to be loaded with high levels of calcium and phosphorous, confirming that calcium phosphate had been deposited in each case. Samples were also subjected to XRD analysis. In each case, the analysis detected only peaks associated with titanium and the calcium phosphate deposit. Analysis of the ratio of the intensity of the HA (211) peak to the intensity of the Ti (101) peak showed approximately equivalent signals for all samples.
  • the adhesion of the deposited material was measured using a test method based on ASTM F1147. This determined that the adhesion of the deposit was in excess of 58 MPa, which was the failure point of the adhesive.
  • the maximum adhesion measured for the shot peen samples was also measured and an average value of 25 MPa was recorded. This is significantly below the level measured for the samples deposited using an abrasive, thereby confirming that the samples produced by abrasive blasting had a much stronger adhesive bond to the substrate, as would be expected from a chemically bonded material.
  • a series of 1 mm thick Grade 5 titanium samples were subjected to abrasive bombardment using a 50:50 mixture of 100 micron alumina abrasive and hydroxyapatite (25-60 microns particle distribution) and a bombardment height of 41 mm.
  • Particle image velocimetry was used to quantify the velocity of the bombarding particles.
  • the samples were subject to bombardment at various particle velocities and the surface of the blasted substrates was then subjected to 5 minutes cleaning in an ultrasonic bath filled with deionised water.
  • the samples were air dried and then analysed using SEM-EDX. Signals arising from lighter element such as carbon and oxygen were not measured and instead the analysis focussed on the heavier elements of Ca, P and Ti.
  • PTFE Polytetrafluoroethylene
  • Example (b) and (c) in Figure 6 were examined using a variety of techniques: microscopy, surface roughness, wear testing and flexural tests, for which the results are shown in Figure 6 . It can be seen that the CoBlast coated samples (samples (b) and (c) in Figure 6 ) had an adherent coating with a significant resistance to wear compared to the samples coated with PTFE only (sa) in Figure 6 ). This study indicates that the CoBlast process can successfully be used to deposit thin adherent coatings of PTFE onto the surface of superelastic NiTi.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Chemically Coating (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP21208806.6A 2015-09-28 2016-09-28 Modification de surfaces par projection abrasive Active EP3978191B1 (fr)

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GBGB1517128.3A GB201517128D0 (en) 2015-09-28 2015-09-28 Abrasive blast modification of surfaces
EP16777957.8A EP3356082B1 (fr) 2015-09-28 2016-09-28 Modification de projection abrasive de surfaces
PCT/EP2016/073155 WO2017055376A1 (fr) 2015-09-28 2016-09-28 Modification de projection abrasive de surfaces

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GB202004947D0 (en) * 2020-04-03 2020-05-20 Rolls Royce Plc Joining component bodies
CN112379472B (zh) * 2020-11-13 2022-08-16 上海卫星装备研究所 一种低吸辐比的光学太阳反射镜及其制备方法
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KR102433787B1 (ko) * 2022-03-17 2022-08-18 주식회사 세기엔지니어링 드라이아이스 기반의 복합 블라스트 처리 공법
KR102485983B1 (ko) * 2022-07-14 2023-01-06 주식회사 세기엔지니어링 흡입력을 강화한 건식 블라스트 공법
TWI824695B (zh) * 2022-09-05 2023-12-01 國立臺灣科技大學 用以提升研磨拋光性能之研磨墊修整裝置、製造修整裝置的方法、修整的方法及研磨的方法
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JP2018535836A (ja) 2018-12-06
EP3356082B1 (fr) 2021-12-29
CN108136566A (zh) 2018-06-08
KR102602557B1 (ko) 2023-11-14
EP3356082A1 (fr) 2018-08-08
CA2998552A1 (fr) 2017-04-06
MX2018003727A (es) 2018-09-12
US20180282874A1 (en) 2018-10-04
KR20180061176A (ko) 2018-06-07
MY191014A (en) 2022-05-28
AU2016329103A1 (en) 2018-04-05
GB201517128D0 (en) 2015-11-11
EP3978191B1 (fr) 2024-08-07
US20220170163A1 (en) 2022-06-02
WO2017055376A1 (fr) 2017-04-06
RU2018114629A (ru) 2019-10-30

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