EP2652169A1 - Procédé de traitement plasma de pièces et pièce comportant une couche barrière aux gaz - Google Patents
Procédé de traitement plasma de pièces et pièce comportant une couche barrière aux gazInfo
- Publication number
- EP2652169A1 EP2652169A1 EP11831820.3A EP11831820A EP2652169A1 EP 2652169 A1 EP2652169 A1 EP 2652169A1 EP 11831820 A EP11831820 A EP 11831820A EP 2652169 A1 EP2652169 A1 EP 2652169A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- plasma
- workpiece
- protective layer
- barrier layer
- gas
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 61
- 230000004888 barrier function Effects 0.000 title claims abstract description 40
- 238000009832 plasma treatment Methods 0.000 title claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 51
- 239000010410 layer Substances 0.000 claims abstract description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011241 protective layer Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 229910052786 argon Inorganic materials 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 4
- 239000012815 thermoplastic material Substances 0.000 claims description 4
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical 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
- C23C16/50—Chemical 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 using electric discharges
- C23C16/511—Chemical 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 using electric discharges using microwave discharges
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical 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
- C23C16/50—Chemical 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 using electric discharges
- C23C16/515—Chemical 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 using electric discharges using pulsed discharges
Definitions
- the invention relates to a method for plasma treatment of workpieces, in which the workpiece is inserted into a plasma chamber and in which subsequently a coating is deposited on the workpiece under the influence of a negative pressure after the ignition of a plasma and in which the ignition of the plasma by microwave energy takes place, wherein the coating consists of at least a gas barrier layer and a protective layer.
- the invention further relates to a workpiece made of a thermoplastic material which is provided in the region of at least one surface with a gas barrier layer deposited from a plasma containing SiOx and at on the gas barrier layer, a protective layer is disposed, which contains carbon.
- Such methods are used, for example, to provide plastics with surface coatings.
- such devices are already known to coat inner or outer surfaces of containers intended for packaging liquids.
- facilities for plasma sterilization are known.
- PCT WO 95/22413 describes a plasma chamber for the inner coating of PET bottles.
- the bottles to be coated are raised by a movable floor in a plasma chamber and brought in the area of a bottle mouth with an adapter in combination. Through the adapter, an evacuation of the bottle interior can take place.
- a hollow gas lance is inserted through the adapter into the interior of the bottles to supply process gas. Ignition of the plasma occurs using a microwave.
- EP-OS 10 10 773 a feeder is described to evacuate a bottle interior and to supply with process gas.
- PCT-WO 01/31680 a plasma chamber is described in which the bottles are introduced by a movable lid which has been previously connected to a mouth region of the bottles.
- PCT-WO 00/58631 also already shows the arrangement of plastifications on a rotating wheel and describes for such an arrangement a group assignment of vacuum pumps and plasma stations in order to promote a favorable evacuation of the chambers and the interiors of the bottles.
- the coating of several containers in a common plasma station or a common cavity is mentioned.
- a gas lance is described, which is retractable into the interior of a preform to be coated and serves for the supply of process gases.
- the gas lance is positionable in the longitudinal direction of the container.
- WO 03/014412 Al the implementation of a plasma coating process is described in which the required energy input by pulsed microwave energy he follows. For the entire implementation of the coating process, a suitable pulse width and pulse height for the microwave energy is selected. Also, pause times are set between the individual pulses and kept constant for the duration of the coating. Is varied according to this prior art in the implementation of the coating process, the volume flow of supplied process gases and the mixture of process gases. Typically, the mixing ratios and / or the respective volume flows of the process gases are switched over at specific times, so that a multilayer layer structure results.
- SiO x barrier layers are applied to a plastic substrate, two layers are typically generated, namely an adhesive layer and the actual barrier layer. Depending on the application, an additional protective layer can be arranged on the barrier layer.
- the process gases used include, for example, HMDSO or HMDSN to provide the silicon and oxygen as the oxidizing gas.
- the properties of each deposited layer and in particular the carbon content is controlled by the amount of oxygen supplied and / or the way in which the microwave energy is introduced.
- the previous methods can not yet meet all requirements.
- the delivery of undesirable substances that alter the taste to the bottled product can not be completely ruled out, moreover, the requirements for the protective layer against resistance are constantly increasing, in particular requirements for a resistance to pH values in the basic range.
- the object of the present invention is therefore to improve a method of the aforementioned type such that the properties of the protective layer are improved.
- the protective layer is produced from a gas containing at least one silicon compound and argon.
- Another object of the present invention is to provide a workpiece of the aforementioned type such that the protective layer has improved properties.
- the protective layer contains argon.
- argon as a process gas in the production of the protective layer on the one hand reduces the production of taste perceptible substances.
- it is particularly intended to substitute for the production of the protective layer by the argon, the use of oxygen or at least to reduce the amount of oxygen. It can be seen that the protective layer is improved both in terms of its resistance to external influences as well as other properties compared to the prior art.
- HMDSO is used as a process gas.
- HMDSN is used as a process gas. Controllability of the process is aided by using a pulsed microwave to ignite the plasma.
- a simple process execution can be achieved by supplying the process gases with a temporally substantially constant volume flow during the production of the protective layer.
- Particularly advantageous properties can be achieved by depositing carbon in a proportion of about 30 to 60 element percent in the protective layer.
- the method according to the invention is particularly suitable for influencing the course of a coating process for plastic bottles.
- an internal coating of these bottles with a layer of SiOx takes place, wherein the adhesion of the layer of SiOx on the plastic can be improved by an intermediate layer, which is formed as an adhesion promoter.
- the coating process is preferably carried out as a PICVD plasma process (plasma impulse induced chemical vapor deposition).
- the plasma is ignited using pulses from a microwave.
- the pulses can be controlled with regard to their pulse width, the pulse spacing and the pulse height.
- 1 is a schematic diagram of a plurality of plasma chambers, which are arranged on a rotating plasma wheel and in which the plasma wheel is coupled to input and output wheels, 2 shows an arrangement similar to FIG. 1, in which the plasma stations are each equipped with two plasma chambers,
- FIG. 3 is a perspective view of a plasma bath with a plurality of plasma chambers
- FIG. 4 is a perspective view of a plasma station with a cavity
- FIG. 5 is a front view of the apparatus of FIG. 4 with the plasma chamber closed
- FIG. 6 shows a cross section according to section line VI-VI in FIG.
- FIG. 7 is a partial representation of a cross section through a substrate with a barrier layer
- FIG. 10 process data for generating a barrier layer for the process variants according to FIG. 8, FIG.
- FIG. 11 process data for generating a protective layer for the process variants according to FIG. 8, FIG.
- Fig. 12 is a diagram for comparing barrier properties of barrier layers, which by the different process gas compositions were deposited as shown in FIG. 8 and
- Fig. 13 is a greatly enlarged cross-section through a
- FIG. 1 shows a plasma module (1), which is provided with a rotating plasma wheel (2). Along a circumference of the plasma wheel (2) a plurality of plasma stations (3) are arranged. The plasma stations (3) are provided with cavities (4) or plasma chambers (17) for receiving workpieces (5) to be treated.
- the workpieces (5) to be treated become the plasma module
- the input wheel (11) transfers the workpieces (5) to be treated to the plasma wheel (2).
- the treated workpieces (5) are removed from the area of the plasma wheel (2) by an output wheel (12) and transferred to the area of an output line (13).
- the plasma stations (3) are each equipped with two cavities (4) or plasma chambers (17). This allows each two workpieces (5) treated simultaneously.
- Fig. 3 shows a perspective view of a plasma module (1) with partially constructed plasma wheel (2).
- the plasma stations (3) are arranged on a support ring (14), which is formed as part of a rotary joint and mounted in the region of a machine base (15).
- the plasma stations (3) each have a station frame (16) which holds plasma chambers (17).
- the plasma chambers (17) have cylindrical chamber walls (18) and microwave generators (19).
- a rotary distributor (20) is arranged, via which the plasma stations (3) are supplied with resources and energy.
- ring lines (21) can be used.
- the workpieces (5) to be treated are shown below the cylindrical chamber walls (18). Parts of the plasma chambers (17) are not shown for simplicity.
- Fig. 4 shows a plasma station (3) in a perspective view. It can be seen that the station frame (16) is provided with guide rods (23) on which a Carriage (24) for supporting the cylindrical chamber wall (18) is guided. Fig. 4 shows the carriage (24) with chamber wall (18) in a raised state, so that the workpiece (5) is released. in the upper region of the plasma station (3) of the microwave generator (19) is arranged.
- the microwave generator (19) is connected via a deflection (25) and an adapter (26) to a coupling channel (27), which opens into the plasma chamber (17).
- the microwave generator (19) both directly in the region of the Kammerdek- (31) and via a spacer element to the chamber lid (31) coupled with a predetermined distance to the chamber lid (31) and thus in a larger surrounding area of the chamber lid (31) to be ordered.
- the adapter (26) has the puncture of a transition element and the coupling channel (27) is formed as a coaxial conductor, in the region of an opening of the coupling channel (27) in the chamber lid (31) is arranged a quartz glass window.
- the deflection (25) is designed as a waveguide.
- the workpiece (5) is positioned by a holding element (28), which is arranged in the region of a chamber bottom (29).
- the chamber bottom (29) is formed as part of a chamber base (30).
- Another variant is to attach the chamber base (30) directly to the station frame (16). With such an arrangement, it is also possible, for example, to make the guide rods (23) in two parts in the vertical direction.
- FIG. 5 shows a front view of the plasma station (3) according to FIG. 3 in a closed state of the plasma chamber (17).
- the carriage (24) with the cylindrical chamber Wall (18) is in this case lowered relative to the positioning in Fig. 4, so that the chamber wall (18) is moved against the chamber bottom (29). In this positioning state, the plasma coating can be performed.
- the coupling channel (27) opens into a comb deekel (31) having a laterally projecting flange (32), in the region of the flange ( 32), a seal (33) is arranged, which is acted upon by an inner flange (34) of the chamber wall (18). In a lowered state of the chamber wall (18), this results in a sealing of the chamber wall (18) relative to the chamber lid (31).
- a further seal (35) is arranged in a lower region of the chamber wall (18) in order to ensure a seal relative to the chamber bottom (29).
- the chamber wall (18) surrounds the cavity (4), so that both an interior of the cavity (4) and an interior of the workpiece (5) can be evacuated.
- a hollow gas lance (36) is arranged in the region of the chamber cup (30) and can be moved into the interior of the workpiece (5).
- this is supported by a lance carriage (37) which can be positioned along the guide rods (23).
- a process gas channel (38) Within the lance carriage (37) extends a process gas channel (38), which is coupled in the raised position shown in Fig. 6 with a gas port (39) of the chamber base (30).
- the workpiece (5) into a plasma chamber (17) immovable relative to the associated support structure. It is also possible, as an alternative to the illustrated coating of the workpieces (5) with their mouths in the vertical direction downward to perform a coating of the workpieces with their mouths in the vertical direction upward, in particular, it is conceived, a coating of flaschenförmigen workpieces (5 ).
- Such bottles are also preferably formed of a thermoplastic material, preferably is intended to the use of PET or PP. According to a further preferred embodiment, the coated bottles serve to receive drinks.
- a typical treatment process is explained below using the example of a coating process and carried out such that first the workpiece (5) using the input wheel (11) to the plasma wheel (2) is transported and that in a pushed-up state of the sleeve-like chamber wall (18) Insertion of the workpiece (5) in the plasma station (3) takes place. After completion of the insertion process, the chamber wall (18) is lowered into its sealed positioning and initially carried out simultaneously an evacuation of both the cavity (4) and an interior of the workpiece (5).
- the lance (36) is retracted into the interior of the workpiece (5) and by a displacement of the holding element (28) a foreclosure of the interior of the workpiece (5) relative to the interior of the cavity ( 4). It is also possible to use the gas lance (36) already in sync with the beginning evacuation of the interior of the cavity in the workpiece (5) to move into. The pressure in the interior of the workpiece (5) is then further lowered. In addition, it is also intended to carry out the positioning movement of the gas lance (36) at least partially already parallel to the positioning of the chamber wall (18). After reaching a sufficiently low negative pressure process gas is introduced into the interior of the workpiece (5) and ignited with the aid of the microwave generator (19) the plasma. In particular, it is envisaged to deposit both an adhesion promoter on an inner surface of the workpiece (5) and the actual barrier layer of silicon oxides with the aid of the plasma.
- the gas lance (36) is again removed from the interior of the workpiece (5) and the plasma chamber (17) and the interior of the workpiece (5) are vented. After reaching the ambient pressure within the cavity (4), the chamber wall (18) is lifted again to carry out a removal of the coated workpiece (5) and an input of a new workpiece to be coated (5).
- a positioning of the chamber wall (18), the sealing element (28) and / or the gas lance (36) can be carried out using different drive units.
- it is intended to realize a cam control in support of an exact coordination of movement with a rotation of the plasma wheel (2).
- the curve control can for example be designed such that along a Circumference of the plasma wheel (2) cams are arranged along which cam rollers are guided. The cam rollers are coupled to the respective components to be positioned.
- Fig. 7 shows a partial view of an enlarged cross-section through a workpiece (5) which is provided with a barrier layer (40).
- the barrier layer (40) is disposed on a wall of a bottle-shaped container.
- the workpiece (5) consists of PET.
- the barrier layer (40) is preferably connected to the workpiece (5) via an adhesive layer (41).
- the adhesion layer (41) and / or the protective layer (42) may be formed as layers delimited by the barrier layer (40), but in particular it is intended to realize so-called gradient layers in which a layer-like effect is achieved by a change in the elemental composition a layer thickness (43) is achieved.
- so-called gradient layers are provided.
- Affected by the change in the elemental composition is at least one of the chemical elements carbon, silicon and oxygen. In principle, however, other chemical elements can additionally or alternatively be used.
- Fig. 8 shows different process parameters for eight different samples.
- sample numbers S 5512 to S 5514 a process is carried out in which both the adhesive layer (41) and the barrier layer (40) and the protective layer (42) in the presence of oxygen as a pro be separated off gas.
- sample number n S 5514 to s 5517 both the adhesive layer (41) and the protective layer (42) are deposited in the presence of argon.
- sample number S 5518 the adhesion layer (41) is deposited in the presence of oxygen and the deposition of the protective layer (42) in the presence of argon.
- the adhesion layer (41) is deposited in the presence of oxygen and no protective layer (42) is applied.
- Each bottle is made for hot filling.
- Fig. 9 shows the process parameters for the application of the adhesive layer (41) for the sample numbers shown in Fig. 8.
- the pulse times are based on the pulse width of the ignited microwave pulses and the pause times on the distances between the individual microwave pulses. Entered are also the microwave power and the applied process pressure. Also, the flow is listed for HMDSO as well as for oxygen and argon, respectively.
- FIG. 12 shows as a bar chart the barrier properties of the samples according to FIG. 8. It can be seen in principle that with increasing storage time, the barrier properties decrease. In addition, it can be seen that the barrier properties are significantly better in a deposition of the protective layer (42) in the presence of argon as the barrier properties of deposition of the protective layer (42) in the presence of oxygen. In particular, it proved to be advantageous to deposit both the adhesive layer (41) and the protective layer (42) in the presence of argon.
- FIG. 13 shows a further enlarged partial cross section through a workpiece (5) with a barrier layer (40).
- a curve of the carbon concentration over the layer thickness (43) is entered in elemental percent.
- the functional properties of the adhesive layer (41) and / or the protective layer (42) are achieved by a change in the elemental composition.
- the carbon content in elemental percent in the region of the functional adhesive layer (41) and / or the functional protective layer (42) is in the range of 10 to 60 element percent.
- the protective layer (42) is a value of about 30 to 60 element percent.
- the carbon content in the range of the functional barrier properties is about 5 element percent.
- a silicon-containing gas and argon, but no oxygen is supplied in the production of the adhesive layer (41).
- the silicon contained gas and oxygen, but no argon is supplied in the formation of the barrier layer (40).
- the silicon contained gas and oxygen, but no argon is supplied in the preparation of the protective layer (42) then the silicon contained gas and argon, but no oxygen is supplied again.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
L'invention concerne un procédé de traitement plasma de pièces selon lequel la pièce est logée dans une chambre d'une station de traitement, dans laquelle le vide peut être réalisé au moins partiellement. La chambre plasma est délimitée par une base, un élément de recouvrement et une paroi latérale. Le traitement plasma permet de déposer un revêtement sur la pièce. L'allumage du plasma est réalisé au moyen d'énergie micro-ondes. Le revêtement est composé d'au moins une couche barrière aux gaz et d'une couche de protection. La couche barrière aux gaz contient SiOx et la couche de protection contient du carbone. La couche de protection est produite à partir d'un gaz contenant au moins un composé silicium ainsi que de l'argon.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010055155A DE102010055155A1 (de) | 2010-12-15 | 2010-12-15 | Verfahren zur Plasmabehandlung von Werkstücken sowie Werkstück mit Gasbarriereschicht |
| PCT/DE2011/002159 WO2012089196A1 (fr) | 2010-12-15 | 2011-12-15 | Procédé de traitement plasma de pièces et pièce comportant une couche barrière aux gaz |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2652169A1 true EP2652169A1 (fr) | 2013-10-23 |
Family
ID=45936583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11831820.3A Withdrawn EP2652169A1 (fr) | 2010-12-15 | 2011-12-15 | Procédé de traitement plasma de pièces et pièce comportant une couche barrière aux gaz |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20130264303A1 (fr) |
| EP (1) | EP2652169A1 (fr) |
| JP (1) | JP2013545897A (fr) |
| DE (1) | DE102010055155A1 (fr) |
| WO (1) | WO2012089196A1 (fr) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK2251454T3 (da) | 2009-05-13 | 2014-10-13 | Sio2 Medical Products Inc | Coating og inspektion af beholder |
| US11624115B2 (en) | 2010-05-12 | 2023-04-11 | Sio2 Medical Products, Inc. | Syringe with PECVD lubrication |
| US9878101B2 (en) | 2010-11-12 | 2018-01-30 | Sio2 Medical Products, Inc. | Cyclic olefin polymer vessels and vessel coating methods |
| DE102011104730A1 (de) * | 2011-06-16 | 2012-12-20 | Khs Corpoplast Gmbh | Verfahren zur Plasmabehandlung von Werkstücken sowie Werkstück mit Gasbarriereschicht |
| AU2012318242A1 (en) | 2011-11-11 | 2013-05-30 | Sio2 Medical Products, Inc. | Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus |
| US11116695B2 (en) | 2011-11-11 | 2021-09-14 | Sio2 Medical Products, Inc. | Blood sample collection tube |
| US20150297800A1 (en) | 2012-07-03 | 2015-10-22 | Sio2 Medical Products, Inc. | SiOx BARRIER FOR PHARMACEUTICAL PACKAGE AND COATING PROCESS |
| WO2014078666A1 (fr) | 2012-11-16 | 2014-05-22 | Sio2 Medical Products, Inc. | Procédé et appareil pour détecter des caractéristiques d'intégrité de revêtement de barrière rapide |
| EP2925903B1 (fr) | 2012-11-30 | 2022-04-13 | Si02 Medical Products, Inc. | Contrôle de l'uniformité de dépôt chimique en phase vapeur activé par plasma (pecvd) sur des seringues médicales, des cartouches et analogues |
| US9764093B2 (en) | 2012-11-30 | 2017-09-19 | Sio2 Medical Products, Inc. | Controlling the uniformity of PECVD deposition |
| CN105392916B (zh) | 2013-03-11 | 2019-03-08 | Sio2医药产品公司 | 涂布包装材料 |
| US9937099B2 (en) | 2013-03-11 | 2018-04-10 | Sio2 Medical Products, Inc. | Trilayer coated pharmaceutical packaging with low oxygen transmission rate |
| EP2971227B1 (fr) | 2013-03-15 | 2017-11-15 | Si02 Medical Products, Inc. | Procede de revetement. |
| EP3693493A1 (fr) | 2014-03-28 | 2020-08-12 | SiO2 Medical Products, Inc. | Revêtements antistatiques pour récipients en plastique |
| US11077233B2 (en) | 2015-08-18 | 2021-08-03 | Sio2 Medical Products, Inc. | Pharmaceutical and other packaging with low oxygen transmission rate |
| DE102016105548A1 (de) | 2016-03-24 | 2017-09-28 | Khs Plasmax Gmbh | Verfahren und Vorrichtung zur Plasmabehandlung von Behältern |
| USD977142S1 (en) | 2016-08-18 | 2023-01-31 | Sio2 Medical Products, Inc. | Vial |
| USD962466S1 (en) | 2019-11-06 | 2022-08-30 | Sio2 Medical Products, Inc. | Collection tube assembly |
| USD948743S1 (en) | 2019-11-06 | 2022-04-12 | Sio2 Medical Products, Inc. | Collection tube assembly |
| CH717298A1 (de) * | 2020-04-06 | 2021-10-15 | Ruggli Projects Ag | Vorrichtung und Verfahren zum Fügen mehrteiliger Tampon-Applikatoren. |
| US20230290616A1 (en) * | 2022-03-11 | 2023-09-14 | Applied Materials, Inc. | Semiconductor chamber components with multi-layer coating |
| DE102023132995A1 (de) * | 2023-11-27 | 2025-05-28 | Khs Gmbh | Verfahren zum Beschichten von Mehrwegbehältern, nach diesem Verfahren hergestellte Behälter und Behälterbeschichtungsmaschine zum Beschichten von Mehrweg-Kunststoffbehältern |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0693975B2 (fr) | 1994-02-16 | 2003-07-30 | The Coca-Cola Company | Recipients creux a revetement interieur inerte ou impermeable applique par reaction superficielle au plasma ou polymerisation superficielle |
| AU744162B2 (en) | 1997-02-19 | 2002-02-14 | Kirin Beer Kabushiki Kaisha | Method and apparatus for producing plastic container having carbon film coating |
| CA2304613A1 (fr) | 1997-09-30 | 1999-04-08 | Jacques Laurent | Procede et appareil pour le traitement de la surface interieure de bouteilles en plastique, dans un procede active par plasma |
| EP0926731A1 (fr) * | 1997-12-18 | 1999-06-30 | STMicroelectronics S.r.l. | Procédé de passivation finale de circuits intégrés |
| DE19901834A1 (de) * | 1999-01-19 | 2000-07-20 | Leybold Systems Gmbh | Verfahren zum Beschichten von Substraten aus Kunststoff |
| FR2791598B1 (fr) | 1999-03-30 | 2001-06-22 | Sidel Sa | Machine a carrousel pour le traitement de corps creux comportant un circuit de distribution de pression perfectionne et distributeur pour une telle machine |
| FR2799994B1 (fr) | 1999-10-25 | 2002-06-07 | Sidel Sa | Dispositif pour le traitement d'un recipient a l'aide d'un plasma a basse pression comportant un circuit de vide perfectionne |
| DE10138697B4 (de) | 2001-08-07 | 2005-02-24 | Schott Ag | Verfahren und Vorrichtung zum Beschichten und Spritzblasen eines dreidimensionalen Körpers |
| DE10138696A1 (de) * | 2001-08-07 | 2003-03-06 | Schott Glas | Verfahren und Vorrichtung zum gleichzeitigen Beschichten und Formen eines dreidimensionalen Körpers |
| DE10253512A1 (de) * | 2002-11-16 | 2004-06-03 | Schott Glas | Rundläufermaschine für CVD-Beschichtungen |
| US7810448B2 (en) * | 2002-05-24 | 2010-10-12 | Schott Ag | Apparatus and method for the treating of workpieces |
| DE10258681A1 (de) * | 2002-08-07 | 2004-02-26 | Schott Glas | Verfahren zum Herstellen von glatten Barriereschichten und Verbundmaterial mit glatter Barriereschicht |
| WO2003100121A2 (fr) * | 2002-05-24 | 2003-12-04 | Schott Ag | Dispositif d'application de revetement multiplace et procede d'application de revetement par plasma |
| US7758936B2 (en) * | 2003-09-18 | 2010-07-20 | Boehringer Ingelheim Gmbh | Pharmaceutical blister |
| JP4711285B2 (ja) * | 2004-03-26 | 2011-06-29 | 株式会社吉野工業所 | 高いガスバリア性を有する合成樹脂製容器 |
| DE102004017241B4 (de) * | 2004-04-05 | 2012-09-27 | Schott Ag | Verbundmaterial und Verfahren zu seiner Herstellung |
| DE102004020185B4 (de) | 2004-04-22 | 2013-01-17 | Schott Ag | Verfahren und Vorrichtung für die Innenbeschichtung von Hohlkörpern sowie Verwendung der Vorrichtung |
| DE102004028369B4 (de) * | 2004-06-11 | 2007-05-31 | Schott Ag | Verfahren und Vorrichtung zum Behandeln von Substraten in einer Rundläuferanlage |
| JP4747605B2 (ja) * | 2005-02-22 | 2011-08-17 | 東洋製罐株式会社 | プラズマcvd法による蒸着膜 |
| DE102005040266A1 (de) * | 2005-08-24 | 2007-03-01 | Schott Ag | Verfahren und Vorrichtung zur innenseitigen Plasmabehandlung von Hohlkörpern |
| JP5275543B2 (ja) * | 2005-08-31 | 2013-08-28 | 株式会社吉野工業所 | 高いバリア性を有する合成樹脂製容器 |
| DE102006048658B4 (de) * | 2006-10-14 | 2014-03-27 | Khs Corpoplast Gmbh | PICVD-Beschichtung für Kunststoffbehälter und Verfahren zu deren Herstellung |
| JP5250958B2 (ja) * | 2006-10-18 | 2013-07-31 | 凸版印刷株式会社 | プラスチック容器及びプラスチック容器の製造方法 |
| ITMI20062482A1 (it) * | 2006-12-22 | 2007-03-23 | Ce S I Centro Studi Industriali Di Taddei Ing | Rivestimento ibrido idrorepellente e impermeabile all'umidita' per materiali compositi polimerici rinforzati deposto mediante pecvd |
-
2010
- 2010-12-15 DE DE102010055155A patent/DE102010055155A1/de not_active Withdrawn
-
2011
- 2011-12-15 WO PCT/DE2011/002159 patent/WO2012089196A1/fr not_active Ceased
- 2011-12-15 JP JP2013543528A patent/JP2013545897A/ja active Pending
- 2011-12-15 US US13/993,778 patent/US20130264303A1/en not_active Abandoned
- 2011-12-15 EP EP11831820.3A patent/EP2652169A1/fr not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2012089196A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013545897A (ja) | 2013-12-26 |
| WO2012089196A9 (fr) | 2012-09-07 |
| DE102010055155A1 (de) | 2012-06-21 |
| WO2012089196A1 (fr) | 2012-07-05 |
| US20130264303A1 (en) | 2013-10-10 |
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