WO2017021407A1 - Insert revêtu pour extrudeuse alimentaire - Google Patents

Insert revêtu pour extrudeuse alimentaire Download PDF

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Publication number
WO2017021407A1
WO2017021407A1 PCT/EP2016/068425 EP2016068425W WO2017021407A1 WO 2017021407 A1 WO2017021407 A1 WO 2017021407A1 EP 2016068425 W EP2016068425 W EP 2016068425W WO 2017021407 A1 WO2017021407 A1 WO 2017021407A1
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WO
WIPO (PCT)
Prior art keywords
insert
process according
coating
metal
source
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PCT/EP2016/068425
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English (en)
Inventor
Giancarlo ADDARIO
Italo Bardiani
Manuel Mariani
Mariangiola BRISOTTO
Laura Borgese
Original Assignee
Barilla G. E R. Fratelli S.P.A.
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.)
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Application filed by Barilla G. E R. Fratelli S.P.A. filed Critical Barilla G. E R. Fratelli S.P.A.
Publication of WO2017021407A1 publication Critical patent/WO2017021407A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523Pulsed gas flow or change of composition over time
    • C23C16/45525Atomic layer deposition [ALD]
    • C23C16/45555Atomic layer deposition [ALD] applied in non-semiconductor technology
    • AHUMAN NECESSITIES
    • A21BAKING; EDIBLE DOUGHS
    • A21CMACHINES OR EQUIPMENT FOR MAKING OR PROCESSING DOUGHS; HANDLING BAKED ARTICLES MADE FROM DOUGH
    • A21C11/00Other machines for forming the dough into its final shape before cooking or baking
    • A21C11/16Extruding machines
    • AHUMAN NECESSITIES
    • A21BAKING; EDIBLE DOUGHS
    • A21CMACHINES OR EQUIPMENT FOR MAKING OR PROCESSING DOUGHS; HANDLING BAKED ARTICLES MADE FROM DOUGH
    • A21C3/00Machines or apparatus for shaping batches of dough before subdivision
    • A21C3/04Dough-extruding machines ; Hoppers with moving elements, e.g. rollers or belts as wall elements for drawing the dough
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/401Oxides containing silicon
    • C23C16/402Silicon dioxide
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/405Oxides of refractory metals or yttrium
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1655Process features
    • C23C18/1662Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

Definitions

  • the present invention relates in general terms to a process for coating inserts for a die for food products, for example pasta, by means of atomic layer deposition (ALD) technique or by means of a liquid phase autocatalytic deposition technique.
  • ALD atomic layer deposition
  • liquid phase autocatalytic deposition technique a liquid phase autocatalytic deposition technique
  • the extrusion of pasta constitutes a crucial step in the production of the pasta itself since, by means of this operation, it is possible not only to determine the shape and thickness of the finished product, but also to provide the extruded product with distinctive characteristics in terms of its surface roughness.
  • the extrusion step is performed by means of the passage of the mixture through inserts which are typically made of brass or teflon or, less frequently, other materials such as steel or gold.
  • inserts typically made of brass or teflon or, less frequently, other materials such as steel or gold.
  • the interaction between material and mixture determines the surface properties of the finished product: teflon allows a pasta with a particularly smooth external surface to be obtained; metals, on the other hand, provide the product with roughness.
  • the atomic layer deposition (ALD) technique is a particular form of chemical vapor deposition (CVD) in which, differently from the latter, the treated substrate is exposed to each reagent separately, and all the reactions involved are limited to the surface.
  • CVD chemical vapor deposition
  • the reagents are fed together into the reaction chamber and may react both in the gaseous phase and on the surface of the substrate, during aggregation and growth.
  • WO 201 1 /099868 describes a die for extruding metallic material, comprising plates with cavities provided with inserts, where the inserts are made of wear-resistant material consisting of steel provided with a coating obtained by means of the CVD technique.
  • WO 2010/024902 describes a die for forming a green ceramic body, provided with a wear-resistant coating consisting of an inorganic nitride or carbide and formed by means of CVD.
  • US 6176153 relates to a disk-shaped die with a shaped opening for the extrusion of metallic material, provided with a metal oxide, nitride or carbide surface coating applied by means of CVD.
  • WO 2008151947 describes an extrusion die orifice for producing honeycomb ceramic bodies, comprising a base plate provided with a hard material coating (nitride, carbide, oxide, etc.) obtained by means of the CVD technique, electroplating, and the like.
  • a hard material coating nitride, carbide, oxide, etc.
  • US 2013/078328 Al discloses a pelletizing ring extrusion die, i.a. for food products, comprising a die body having a plurality of extension holes, wherein each hole comprises a surface with a low-friction coating deposited thereon.
  • the low-friction coating comprises a metal, ceramic or composite and can be applied onto the surface of the extension holes by PVD and CVD methods.
  • US 2008/089970 Al discloses a cutter assembly for an extruder including an elongated extrusion member having an opened feed end. This cutter assembly is used for extruding shaped food pieces.
  • a nidox coating can be applied to a bottom of the elongated extrusion member prior to the formation of the through hole, which forms the die. No mention is made of the technique by which such nidox coating is applied.
  • US 2007/ 178198 Al discloses an apparatus for making variously shaped pastry shells, including an annular baking rim supported on a horizontal lower plate to define an upward-facing female die. The exterior surface of the baking ring can be coated with a non-stick, wear-resistant coating, e.g. PTFE or an oxide of aluminum, for ease of baking and cleanup. None is said about the technique by which such coating is applied.
  • the present invention is able to minimize corrosion and increase the mechanical strength of the material, thus prolonging the working life of the insert and also allows reconditioning of the worn inserts by coating them using liquid phase or vapor phase deposition techniques, with undoubted advantages in terms of environmental sustainability: it is in fact not necessary to produce new inserts, nor dispose of the used inserts nor melt them down in order to recover the material, reducing considerably the amount of energy, material and emissions currently needed in order to restore the standard extrusion conditions.
  • the invention relates to a process for coating an insert for a die for food products, preferably for pasta, by means of surface deposition of one or more coating compositions, optionally alternated, comprising at least: a metal oxide, preferably selected from SiO2, ZrO2, A12O3 and ZnO, a metal nitride or a mixed oxide, by means of atomic layer deposition (ALD) technique or by means of a liquid phase autocatalytic deposition technique.
  • ALD atomic layer deposition
  • the invention relates to a process for coating an insert for a die for food products, preferably for pasta, by means of liquid phase autocatalytic chemical deposition of metal composites, by immersion in a bath containing metal ions, and phosphorus-containing compounds.
  • the invention relates to a process for coating an insert for a die for food products, preferably for pasta, by means of the atomic layer deposition (ALD) technique, said process comprising the steps of: a) exposure of the surface of the insert to a suitable metal source within a reaction chamber of an ALD apparatus; b) evacuation treatment with inert gas; c) obtaining the insert coated with the corresponding metal nitride or oxide by exposing the surface of the insert obtained after step b) to a suitable oxygen or nitrogen source; d) evacuation treatment with inert gas.
  • ALD atomic layer deposition
  • the process of the present invention further comprises a step of exposing said surface of the insert to a source of aluminum ions (Al 3+ ) within the reaction chamber.
  • the invention relates to an insert for a die for food products, preferably for pasta, obtained (or obtainable) with the present process.
  • said insert is made of brass and is coated with one or more coating compositions, optionally alternated, comprising at least one metal oxide preferably selected from S1O2, ZrO2, ZnO, or a mixed oxide, for example Ti-Zn oxide or a metal nitride.
  • mixed oxide an oxide containing two or more metal cations is meant, such as the above-mentioned Ti-Zn oxide.
  • the invention relates to use of the ALD technique for coating an insert for a die for food products, more preferably for pasta.
  • the invention relates to the use of a liquid phase autocatalytic deposition technique for coating an insert for a die for food products, preferably for pasta.
  • Figures la- lb show AFM images of an area equal to 10x10 ⁇ 2 of a silicon substrate (Fig. la) having a thickness of 70 nm, coated with S1O2 (Fig. lb) by means of the ALD technique.
  • Figures 2a-2c show AFM images of a brass substrate (Fig. 2a) coated by means of the ALD technique with ZrO2 (Fig. 2b) and with S1O2 (Fig. 2c). Detailed description
  • the process comprises coating an insert for a food extruder by means of a liquid phase autocatalytic deposition technique, by immersion of the insert to be coated in a bath containing metal ions, preferably Ni 2+ , and phosphorus-containing compounds, preferably hypophosphite.
  • metal ions preferably Ni 2+
  • phosphorus-containing compounds preferably hypophosphite.
  • deposition occurs by means of reduction of the metal ions by the hypophosphite ions, the reaction mechanism resulting in co-deposition of phosphate ions from the associated solution and hydrogen evolution.
  • Deposition takes place at preferred temperatures of between about 40- 100°C and at preferred deposition speeds of between 2-20 ⁇ /h.
  • Deposition may optionally occur in the presence of solid particles of a suitable compound, obtaining in this way the co-deposition of said particles in the Ni-P matrix.
  • said particles are selected from: PTFE, silicon carbide and diamond.
  • the process according to the invention is performed by means of vapor phase deposition and comprises coating an insert for a food die by means of the ALD technique.
  • the process is performed by means of exposure of said insert to a continuous flow of inert gas to which a metal source and then an oxygen or nitrogen (indicated below as oxygen/ nitrogen) source are suitably added.
  • the continuous flow of inert gas may be for example nitrogen or argon and said metal and oxygen/ nitrogen source is added to said continuous flow, for example using electrovalves at exposure time intervals (pulsations) which vary from milliseconds to a few tens of seconds depending for example on the plant, the chamber and the experimental conditions chosen.
  • the invention relates to a process for coating an insert for a die for food products, preferably for pasta, by means of the atomic layer deposition (ALD) technique, said process comprising the steps of: a) chemisorption of molecules containing the metal by means of exposure of the surface of an insert for extruding a food product to a suitable metal source; b) evacuation (or washing) treatment with inert gas; c) formation of an atomic layer of the corresponding metal nitride or oxide by means of exposure of the coated surface obtained after step b) to a suitable oxygen or nitrogen source; and d) final washing or evacuation with inert gas.
  • ALD atomic layer deposition
  • the insert is again subjected to steps a)-d), using the same or also different metal source, for a number of cycles which varies depending on the thickness and the type of final coating composition which is to be obtained.
  • the composition coating the surface of the insert according to the process of the invention comprises at least one metal nitride or oxide.
  • the present process by means of the ALD technique will comprise a first adsorption (or chemisorption) of the surface of the insert with metal atoms, due to the exposure to the chosen metal source, followed by the subsequent formation of the corresponding metal nitride or oxide, due to exposure to the oxygen or nitrogen source.
  • the process will comprise the use of a reactor for ALD deposition able to carry out a first pulsation of the metal source, followed by a time period of a few seconds of evacuation treatment of the chamber inside which the insert adsorbed with metal atoms is treated with inert gas in order to remove traces of metal source which have not been adsorbed or may be present inside the reaction chamber. Subsequently, the exposure of the treated surface to the oxygen or nitrogen source allows the formation of the corresponding metal nitride or oxide in the form of a coating atomic layer.
  • the present process therefore comprises a further evacuation treatment in order to remove any oxygen/ nitrogen source residues, thus allowing steps a)-d) to be repeated, with the execution of different cycles for the deposition of successive atomic layers of coating composition.
  • the coating composition comprises one or more atomic layers of oxides or nitride which are alternated with each other.
  • the coating composition comprises alternate layers of AI2O3 and ZnO.
  • Each cycle for the deposition of an atomic layer lasts about 20-30 seconds and is repeated so as to create a final thickness of the order of tens or hundreds of nanometers.
  • a final coating by means of successive depositions of atomic layers of metal nitride or oxide, which are the same or different from each other, until the desired coating height is reached.
  • a number of hours may be required in order to obtain a coating with heights of at least 10 2 nm, as for example indicated in the accompanying Table 1.
  • the process of the invention it is possible to perform the coating using the ALD technique by means of the selective interaction between the free hydroxyls present on the surface of the insert and the metal source molecules.
  • the free hydroxyls in fact determine the selectivity of the chemisorption reaction of the metal source molecules, which is therefore self-terminating.
  • the first chemisorption terminates and the substrate is subjected to the following step of evacuation and exposure to the oxygen/ nitrogen source as described above.
  • the chemisorption reaction of the oxygen or nitrogen atoms giving rise to the corresponding atomic coatings in the form of oxide or nitride is self-terminating, depending on the metal- containing molecules previously chemisorbed on the surface of the insert.
  • the surface of the insert which is coated with the present process is preferably at least the extruding surface, for example the part of the insert which comes into direct contact with the pasta during the extrusion operation.
  • coating is performed by means of exposure of the entire surface of the insert, namely both the extrusion surface and the remaining surface of the said insert.
  • the metal source is usually a metal, or preferably metallorganic, compound or even more preferably in the form of a liquid at atmospheric pressure and temperature, able to be adsorbed on the surface of the insert and combined with the oxygen and nitrogen source used in the subsequent exposure step.
  • the metal source is suitably added to the continuous flow of inert gas for example by means of electrovalves for exposure times which may vary between 10 milliseconds and 60 seconds depending for example on the extent of the total surface area to be covered, the type of reactor, the process parameters such as the base pressure and temperature, and the mechanism of the reaction between the reagents involved.
  • the metal source is preferably a coordination compound of silicon, zirconium, zinc or aluminum.
  • Preferred silicon compounds are selected from silanes and silanols.
  • said metal source is at least one compound selected from: trimethyl aluminum (TMA), tetrakis dimethylamido zirconium (TDMAZ) and tris(tert- butoxy)silanol (TTBS) and diethylzinc (DEZ), TTBS and TDMAZ being particularly preferred.
  • TMA trimethyl aluminum
  • TDMAZ tetrakis dimethylamido zirconium
  • TTBS tris(tert- butoxy)silanol
  • DEZ diethylzinc
  • TMA will result in the formation of a coating composition comprising Al 2 O 3
  • TDMAZ and TTBS will result in the formation of a coating composition comprising respectively ZrO 2 and, in accordance with a preferred embodiment, S1O2.
  • the silicon sources which can be used in the present process may be molecules able to provide optimum results by means of catalytic activation, by another metal (for example aluminum), of the surface to undergo exposure, and subsequent polymerization of the molecules on the catalytic center.
  • an example of a preferred silicon source is TTBS.
  • TTBS may be conveniently used after activation of the insert surface with a suitable aluminum source, subsequent exposure to the TTBS and polymerization of the TTBS molecules present inside the reaction chamber for the entire duration of the exposure time, by means of interaction with the chemisorbed aluminum.
  • the step of exposure to the metal source according to the present process may comprise a prior exposure to a suitable aluminum source, a subsequent exposure to the metal source, preferably TTBS, followed by polymerization of the TTBS molecules which are bonded to the aluminum atoms chemisorbed on the surface of the insert.
  • a suitable aluminum source preferably TTBS
  • a preferred source of aluminum is trimethyl aluminum (TMA).
  • the exposure of the insert to the aluminum source allows the aluminum atoms to be anchored to the surface of the insert by means of exchange of a metal binder with a hydroxyl group present on the surface of the insert to be coated.
  • the metal source preferably TTBS
  • the metal source will bind to the aluminum adsorbed on the surface of the insert, other metal source molecules may spread and react by means of a combined mechanism (see for example D. Hausmann et al, SCIENCE 2002, Vol. 298, pp 402) creating, by means of repetitive insertions, a siloxane polymer bound to the surface by means of the aluminum.
  • the subsequent interconnection between the molecules of the siloxane polymer by means of elimination of butanol molecules, is responsible for the self-terminating nature of the ALD reaction and the formation of the silica monolayer.
  • the polymerization is particularly useful because, by means of a single cycle, it is possible to deposit a certain number of silica monolayers (also more than 30), each with a thickness of about 0.30-0.40 nm, obtaining, in a single cycle, very high thicknesses for an ALD deposition.
  • the insert is again exposed to the chosen aluminum source and subjected to the exposure and polymerization steps as described above, until a final coating having the required thickness is obtained.
  • the process according to the invention comprises exposure of the substrate to a silicon source, such as a silane, followed by washing with inert gas and exposure to the oxygen source selected from: water, ozone and oxygen plasma.
  • a silicon source such as a silane
  • the oxygen source selected from: water, ozone and oxygen plasma.
  • the metal source is generally liquid and able to be poured out by means of the continuous flow of inert gas which acts, therefore, also as a transportation gas.
  • the experimental times and conditions may be optimized depending on the type of reactors, reagents and substrates.
  • the speed of the gas measured using a flowmeter, may vary between 5 and 100 seem (standard cubic centimeters) in the case of depositions in continuous flow mode and between 1 and 20 seem in exposure mode.
  • the following step of treatment with an inert gas is useful in particular for removing from the chamber the metal source traces which are free and not fixed to the surface, achieving in this way a high degree of homogeneity of the surface coating.
  • an inert gas or evacuation
  • the evacuation treatment with the gas lasts typically a few seconds, for example for an exposure time of between 5 and 60 seconds, depending on the reactor temperature.
  • the insert is subjected to exposure to a suitable oxygen or nitrogen source, also followed by an evacuation treatment using inert gas.
  • a suitable oxygen or nitrogen source is selected from: water, hydrogen peroxide, ozone and oxygen plasma, water being particularly preferred. Therefore, in one embodiment of the invention, preferred coating compositions will comprise silicon or zirconium oxides.
  • the nitrogen source useful for the formation of a coating composition comprising the corresponding metal nitride, it is selected from: ammonia, amines, amides and nitrogen plasma. It should be noted that the process according to the invention may be performed cyclically using self-terminating reactions following the steps a)-d) indicated above, and alternated processes which comprise catalytic polymerization.
  • composition coating the insert according to the present process may be analyzed for example in terms of structure, morphology and chemical composition by means of techniques known in the sector, such as X-ray reflectivity or (micro)diffraction, optical microscopy (OM), atomic-force microscopy (AFM) or ray fluorescence.
  • the images shown in Figures la and lb obtained by means of the AFM technique, show respectively the morphology of the substrate and the coating in the case where the substrate is formed by a monocrystalline Si wafer, with amplification of a selected area of 1.5x1.5 ⁇ 2 .
  • the average roughness calculated over an area of about 10x10 ⁇ 2 is equal to about 2 nm for the coating of S1O2 and 2.5 nm for the uncoated substrate.
  • the analysis shows moreover perfect coverage of the substrate and a good uniformity of the material deposited. It is evident also that the morphology of the coating is very different from the globular morphology of the substrate: the coating is in fact more smooth and more uniform than the uncoated substrate. Similar results were obtained considering a coating containing ZrO2.
  • AFM measurements were also carried out on brass (Fig. 2a-c), these showing a reduction in the surface roughness of the brass substrate as such (Fig. 2a) compared to the substrate coated both with ZrO2 (Fig. 2b) and with SiO 2 , (Fig. 2c).
  • the process according to the invention is performed in temperature and pressure conditions such that gas phase reactions and/ or deposition of precursors in liquid form are substantially avoided. Therefore, in one embodiment, the temperatures of the system are higher than the vaporization temperatures of all the precursors used in the pressure conditions in which the process is performed, in particular of the metal and oxygen/ nitrogen source.
  • the temperatures for exposure of the insert according to the present process by means of ALD i.e. the temperatures of the reaction chamber of the ALD apparatus, are preferably at least 40°C, so as to obtain convenient times for removal of the chosen metal or oxygen source.
  • the temperature of exposure to the oxygen/ nitrogen and metal sources is comprised between about 90°C and 300°C depending, for example, on the process and the mechanism considered.
  • the concept of a temperature window for the ALD processes is known to the person skilled in the art (see for example T. Suntola, mater Sci Rep 1989, Vol. 4, pp. 261) and is used to define the temperature range within which the growth of the coating composition in the form of an atomic layer is linear in relation to the number of cycles.
  • the process for coating the die insert for food products according to the present invention may be performed using apparatus and conditions which are known to the person skilled in the art, for example inside a reactor for ALD deposition at low pressure, preferably in the region of 0.1-5 Torr, or using a system such as the Savannah 100 system made by Ultratech Cambridge Nanotech Inc.
  • the present process may find a convenient application in the industrial sector since it may be used for coating inserts which are known in the art and therefore compatible with the common food extruders for pasta.
  • the possibility of coating inserts using different metal oxides moreover ensures optimum versatility since it is possible to obtain extruded food products having, for example, a different roughness and different surface characteristics depending on the morphology of the coating layer applied.
  • a further substantial advantage of the present process is that, as a result of the present invention, the insert may be reconditioned, thus allowing it to be reused.
  • the insert will therefore have a working life much longer than that of conventional uncoated inserts which, once they become worn and deteriorate to the point that they can no longer be used to optimum effect, are usually disposed of.
  • the coated insert according to the present invention has an extremely long working life since it may be coated and reused whenever required, thus avoiding the need for disposal thereof.
  • the invention relates to a food die insert for pasta, which is coated with a coating composition comprising at least one metal oxide or nitride, preferably obtained (or obtainable) by means of the process according to the invention, as described and claimed here.
  • the insert may be made of brass, or using copper alloys, steel or gold and may be optionally coated with teflon or made of teflon.
  • the insert is made of brass.
  • the composition will cover all or part of the insert, preferably at least the extruding surface of the insert, understood as being the surface which comes into direct contact with the pasta.
  • the present invention may be applied in the industrial sector using apparatuses known in the sector, for example designed for the ALD technique.
  • the insert is preferably coated by means of the ALD technique and even more preferably using a coating composition comprising S1O2. The present invention will now be described by the following experimental part without, however, limiting the scope thereof.
  • EXPERIMENTAL PART Example 1 inserts according to the invention, coated by means of the ALD vapor phase deposition technique using a coating composition comprising S1O2 or Zr02.
  • the metal source used was TTBS and TDMAZ, while the oxygen source was H2O and the Al source was TMA. Nitrogen with 99.999% purity was used as inert gas. Further conditions of the coating process are indicated in Table 1.
  • the insert was subjected to cycles of exposure to TTBS and TMA, or TDMAZ and water, at a temperature of about 200°C for a time period of between 2 and 35 hours.
  • a final coating with a thickness of between about 100 nm and 500 nm comprising S1O2 and ZrO2 was therefore obtained, as indicated in the table.
  • Example la inserts according to the invention, coated by means of liquid phase autocatalytic chemical deposition of Ni-P with added SiC. Inserts made of brass for extruding pasta, having a disk-like or parallelepiped shape, were considered. Deposition of a composite based on Ni-P containing silicon carbide particles with a thickness of 10 ⁇ was performed by means of autocatalytic deposition from baths at 60° C containing hypophosphite and Ni salts.
  • Example 2 wettability tests based on contact angle of some coated inserts according to Example 1 and la.
  • the coated parallelepiped shaped inserts according to Example 1 and la with dimensions 10x24x4 mm and surface roughness not greater than 0.5 ⁇ were subjected to contact angle measurements for evaluation of the surface roughness.
  • the contact angle measured may provide an indication of the roughness of the pasta extruded with the coated insert.
  • the roughness obtained with S1O2 is different from that obtained with ZrO2, while excellent stability and wear-resistance of the coating are maintained.
  • the present process is therefore highly versatile since coatings with a high or also low wettability may be obtained, while maintaining in any case a high wear-resistance and working life.
  • the following measurement parameters were kept constant for all the tests carried out:
  • Table 2 shows the results obtained from the tests carried out. Each value corresponds to the average of 10 tests, including the mean standard deviation.
  • Table 2 results of the angle contact measurements carried out on the coated inserts according to Example 1 COATING/ THICKNESS CONTACT ANGLE ( ⁇ °)
  • the coating of S1O2 greatly increases the wettability of the brass sample, with the contact angle reaching a value of less than 20°.
  • the coating of Zr0 2 does not modify substantially the wettability of the sample compared to the bare brass.
  • a silicon chip with low surface roughness (ideal substrate) with 100 nm of Zr0 2 coating was also sampled using the same ALD and tensiometer measurement conditions, in order to evaluate the contact angle of the coating alone.
  • Zr0 2 produced a contact angle of 95.7 ⁇ 1.2, a further indication of the fact that the Zr0 2 coating on the brass test-piece does not modify its wettability.
  • the coating comprising Ni-P/ SiC reduces the wettability of the brass.
  • Example 3 wear tests by means of pin-on-disk testing of some coated inserts according to Example 1
  • the wear tests consist in assessing the behavior of a coating or a bulk material in predefined load and sliding wear conditions.
  • the pin-on-disk configuration involves the use of a test-piece (disk) on which a constant load (N) perpendicular to the surface of the sample is applied by means of a pin with known geometry (standard ASTM G99-04) .
  • the sliding wear conditions are obtained by rotating the test-piece about its axis with a suitable angular speed for a given number of revolutions.
  • Table 3 shows the results obtained from the pin-on-disk wear tests carried out on disk-shaped coated inserts according to Example 1 with a diameter of 30 mm and height of 3 mm.
  • a comparison between coatings made of the same material and with different thicknesses shows that the coating with a thickness five times greater (500 nm as opposed to 100 nm) has a duration one order of magnitude greater than the other coating.
  • This effect is more marked in coatings based on ZrO2.
  • the coating which has the best properties is S1O2.
  • the S1O2 coating with a thickness of 500 nm at the end of the test proved to be still intact and the brass substrate showed signs of failure.
  • the composite coating Ni-P has a markedly higher duration since the thickness is two orders of magnitude greater than that of ALD coatings.

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  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne généralement un procédé de revêtement d'un insert pour une filière pour produits alimentaires qui peut être utilisée, par exemple, pour l'extrusion de pâtes alimentaires, au moyen d'un dépôt de couche atomique (ALD) ou au moyen d'une technique de dépôt autocatalytique en phase liquide. L'insert revêtu obtenu ainsi est particulièrement avantageux en termes de résistance à l'usure de durabilité au cours du temps, de manière à assurer une polyvalence optimale et la possibilité de recyclage.
PCT/EP2016/068425 2015-08-05 2016-08-02 Insert revêtu pour extrudeuse alimentaire WO2017021407A1 (fr)

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Cited By (1)

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WO2023019080A1 (fr) 2021-08-09 2023-02-16 Exxonmobil Chemical Patents Inc. Dispositif et procédé d'extrusion de polymère avec des éléments de diamant polycristallin

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US20060216548A1 (en) * 2005-03-22 2006-09-28 Ming Mao Nanolaminate thin films and method for forming the same using atomic layer deposition
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WO2008151947A1 (fr) 2007-06-15 2008-12-18 Robert Bosch Gmbh Filière d'extrusion pour réaliser des corps céramiques alvéolaires
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US3851084A (en) * 1972-07-05 1974-11-26 Nabisco Inc Method of producing laminated comestible products
US6176153B1 (en) 1997-09-10 2001-01-23 Wefa Werkzeugfabrik Singen Gmbh Process for manufacturing an extrusion tool using a CVD process
US20080089970A1 (en) 2002-12-30 2008-04-17 Hunter Thomas B Cutter assembly for extruding shaped food pieces
US20060216548A1 (en) * 2005-03-22 2006-09-28 Ming Mao Nanolaminate thin films and method for forming the same using atomic layer deposition
US20070178198A1 (en) 2006-01-30 2007-08-02 Lichtenstein David M Making pastry shells
WO2008151947A1 (fr) 2007-06-15 2008-12-18 Robert Bosch Gmbh Filière d'extrusion pour réaliser des corps céramiques alvéolaires
WO2010024902A2 (fr) 2008-08-28 2010-03-04 Corning Incorporated Revêtements anti-usure pour matrices d'outils
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Publication number Priority date Publication date Assignee Title
WO2023019080A1 (fr) 2021-08-09 2023-02-16 Exxonmobil Chemical Patents Inc. Dispositif et procédé d'extrusion de polymère avec des éléments de diamant polycristallin

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