US20130152383A1 - Moisture resistant layered sleeve heater and method of manufacture thereof - Google Patents
Moisture resistant layered sleeve heater and method of manufacture thereof Download PDFInfo
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- US20130152383A1 US20130152383A1 US13/762,842 US201313762842A US2013152383A1 US 20130152383 A1 US20130152383 A1 US 20130152383A1 US 201313762842 A US201313762842 A US 201313762842A US 2013152383 A1 US2013152383 A1 US 2013152383A1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/27—Sprue channels ; Runner channels or runner nozzles
- B29C45/2737—Heating or cooling means therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/02—Details
- H05B3/04—Waterproof or air-tight seals for heaters
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/40—Heating elements having the shape of rods or tubes
- H05B3/42—Heating elements having the shape of rods or tubes non-flexible
- H05B3/46—Heating elements having the shape of rods or tubes non-flexible heating conductor mounted on insulating base
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/40—Heating elements having the shape of rods or tubes
- H05B3/54—Heating elements having the shape of rods or tubes flexible
- H05B3/58—Heating hoses; Heating collars
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49082—Resistor making
- Y10T29/49083—Heater type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49169—Assembling electrical component directly to terminal or elongated conductor
Definitions
- the present disclosure relates to resistance heaters, such as layered heaters by way of example, and more particularly to an apparatus and method for reducing moisture intrusion into such resistance heaters.
- a layered heater generally comprises layers of different materials, namely, a dielectric and a resistive material, which are applied to a substrate.
- the dielectric material is applied first to the substrate and provides electrical isolation between the substrate and the electrically-live resistive material and also reduces current leakage to ground during operation.
- the resistive material is applied to the dielectric material in a predetermined pattern and provides a resistive heater circuit.
- the layered heater also includes leads that connect the resistive heater circuit to an electrical power source, which is typically cycled by a temperature controller.
- the lead-to-resistive circuit interface is also typically protected both mechanically and electrically from extraneous contact by providing strain relief and electrical isolation through a protective layer. Accordingly, layered heaters are highly customizable for a variety of heating applications.
- Layered heaters may be “thick” film, “thin” film, or “thermally sprayed,” among others, wherein the primary difference between these types of layered heaters is the method in which the layers are formed.
- the layers for thick film heaters are typically formed using processes such as screen printing, decal application, or film dispensing heads, among others.
- the layers for thin film heaters are typically formed using deposition processes such as ion plating, sputtering, chemical vapor deposition (CVD), and physical vapor deposition (PVD), among others.
- deposition processes such as ion plating, sputtering, chemical vapor deposition (CVD), and physical vapor deposition (PVD), among others.
- PVD physical vapor deposition
- thermal spraying processes which may include by way of example flame spraying, plasma spraying, wire arc spraying, and HVOF (High Velocity Oxygen Fuel), among others.
- Thermally sprayed layered heaters are generally formed by spraying molten powder or wire feedstock onto a substrate in the requisite layers as set forth above.
- the molten material impacts the substrate, or layers that have previously been applied over the substrate, resulting in lenticular or lamellar grain structure from the rapid solidification of small globules, flattened from striking a cooler surface at relatively high velocities.
- Due to this resultant grain structure a common characteristic of thermally sprayed heaters is porosity, which can be beneficial in terms of fracture toughness, but also detrimental in terms of moisture absorption. In heater applications, if the thermally sprayed layers absorb an excessive amount of moisture, this moisture can cause the heater to fail during operation by mechanisms such as delaminating the individual layers or interrupting the supply of electrical power, or enabling excessive leakage current to ground.
- Moisture absorption is also an issue in many other types of resistance heaters, and thus improved devices and methods to counteract the adverse affects of moisture on heater performance are continually appreciated in the field of resistance heaters.
- a method of forming a heater assembly comprising: forming a plurality of layers onto a substrate using a thermal spray process, wherein a recessed area for a termination is disposed on the layers; forming electrical terminations proximate the recessed area; securing a protective cover over the layers using a laser welding process, wherein edges of the protective cover are welded circumferentially around raised end portions of the substrate and welded longitudinally along a slotted portion of the substrate; securing a pair of lead wires to the electrical terminations within the recessed area; and securing a lead cap assembly around the pair of lead wires and to the protective cover.
- a method of forming a layered heater assembly comprising: forming a plurality of layers onto a substrate, the plurality of layers including a resistive element layer; forming electrical terminations in contact with the resistive element layer; securing a protective cover over the layers using a laser welding process, wherein edges of the protective cover are welded circumferentially around raised end portions of the substrate and welded longitudinally along a slotted portion of the substrate; securing a pair of lead wires to the electrical terminations; securing a lead cap assembly around the pair of lead wires and to the protective cover using a laser welding process.
- a method of forming a heater assembly comprising: preparing a substrate having an outer surface and a recessed area recessed from the outer surface; thermally spraying a resistive layer on the outer surface of the substrate; forming a pair of terminal pads in the recessed area and connecting the terminal pads to the resistive layer; and securing a protective layer to the substrate to protect the resistive layer and the terminal pads against moisture intrusion.
- FIG. 1 is a perspective view of a heater assembly constructed in accordance with the principles of the present disclosure
- FIG. 2 is an enlarged perspective view of the heater assembly in accordance with the principles of the present disclosure
- FIG. 3 is an exploded perspective view of the heater assembly in accordance with the principles of the present disclosure
- FIG. 4 is a top view of the heater assembly in accordance with the principles of the present disclosure.
- FIG. 5 a is a longitudinal cross-sectional view, taken along line A-A of FIG. 4 , illustrating an internal construction of the heater assembly in accordance with the principles of the present disclosure
- FIG. 5 b is a detail view, within view B-B of FIG. 5 a , illustrating various layers of the heater assembly and constructed in accordance with the principles of the present disclosure
- FIG. 6 a is a cross-sectional view, taken along line C-C of FIG. 4 , illustrating a termination area of the heater assembly and constructed in accordance with the principles of the present disclosure
- FIG. 6 b is a detail view, within view D-D of FIG. 6 a , illustrating the layers and terminal pads of the heater assembly and constructed in accordance with the principles of the present disclosure;
- FIG. 7 is a cross-sectional view, taken along line E-E of FIG. 4 , illustrating the termination area and tool supports constructed in accordance with the principles of the present disclosure
- FIG. 8 is a perspective view of a substrate constructed in accordance with the principles of the present disclosure.
- FIG. 9 is a top view of the substrate in accordance with the principles of the present disclosure.
- FIG. 10 is a perspective view of a protective cover constructed in accordance with the principles of the present disclosure.
- FIG. 11 is a perspective view of a lead cap assembly constructed in accordance with the principles of the present disclosure.
- FIG. 12 a is a perspective view of the heater assembly and a set of secondary lead wires constructed in accordance with the principles of the present disclosure
- FIG. 12 b is a partial cross-sectional view of a connection between lead wires using a heat shrink tube and constructed in accordance with the principles of the present disclosure
- FIG. 13 is a plan view of a termination spring constructed in accordance with the principles of the present disclosure.
- FIG. 14 is an enlarged perspective view of lead wires positioned for being secured to a termination spring and constructed in accordance with the principles of the present disclosure.
- FIG. 15 is a flow diagram illustrating a method of manufacturing a heater assembly in accordance with the principles of the present disclosure.
- the heater assembly comprises a substrate 12 , a plurality of layers (not shown) disposed on the substrate that will be described in greater detail below, a protective cover 14 disposed over the layers and secured to the substrate 12 , a pair of lead wires 16 (surrounded by insulation 17 ) secured to the heater assembly 10 , and a lead cap assembly 18 disposed around the pair of lead wires 16 and secured to the protective cover 14 .
- the heater assembly 10 is adapted for use around a target object to be heated such as a hot runner nozzle (not shown) by way of example, hence the geometrical configuration of a cylinder as shown.
- the heater assembly 10 may take other geometrical configurations such as flat, rectangular, or other polygonal shapes while remaining within the scope of the present disclosure. Additionally, although a layered heater construction is employed with the heater assembly 10 as illustrated and described herein, it should be understood that other types of heaters, such as resistive wire, resistive foil, or compacted ceramic, by way of example, may be employed while remaining within the scope of the present disclosure.
- the substrate 12 comprises opposed end portions 20 and 22 that define raised flanges 24 and 26 , respectively.
- a slot 28 extends between the opposed end portions 20 and 22 , and opposed chamfered surfaces 30 and 32 extend along the slot 28 and across the raised flanges 24 and 26 .
- the substrate 12 defines a cylindrical configuration as shown and includes an internal bore 34 that is adapted for placement around a heating target such as a hot runner nozzle, by way of example.
- An outer surface 36 extends between the raised flanges 24 and 26 , and a recess 38 is disposed on the outer surface 36 .
- the recess 38 accommodates a termination area as described in greater detail below.
- the substrate 12 in one form is a stainless steel material, however, it should be understood that a variety of materials may be employed while remaining within the scope of the present disclosure.
- the layers include, by way of example, a first dielectric layer 40 disposed over the substrate 12 and in one form extending between the raised flanges 24 and 26 and proximate the chamfered surfaces 30 and 32 of the substrate 12 .
- the first dielectric layer 40 is also formed over the recess 38 on the substrate 12 , and as such, takes on the form of the recess 38 as shown.
- the first dielectric layer 40 is formed using a thermal spraying process and is generally a constant thickness. It should be understood that other processes and configurations (e.g., variable thickness and/or materials, among others) for the first dielectric layer 40 may be employed while remaining within the scope of the present disclosure.
- a resistive element layer 42 is disposed over the first dielectric layer 40 and may take on the form of a resistive circuit 44 (shown dashed in FIG. 4 ) or may alternately be a continuous layer.
- the resistive element layer 42 is formed using a thermal spraying process and is generally a constant thickness.
- the pattern for the resistive circuit 44 may be formed by any number of methods and in one form is created by using a laser removal process such as that disclosed in copending U.S. application Ser. No. 10/872,752 titled “Method For the Production of an Electrically Conductive Resistive Layer and Heating and/or Cooling Device,” filed on Jun. 21, 2004, which is commonly assigned with the present application and the contents of which are incorporated herein by reference in their entirety.
- the resistive element layer 42 is also formed over the recess 38 on the substrate 12 , and along with the first dielectric layer 40 , takes on the form of the recess 38 as shown.
- a pair of terminal pads 46 are disposed over the first dielectric layer 40 and are in contact with the resistive element layer 42 as shown.
- the terminal pads 46 are adapted for connecting the lead wires 16 , which is described in greater detail below, for the application of electrical power to the heater assembly 10 .
- the terminal pads 46 are created by a thermal spraying process, however, it should be understood that other processes may be employed while remaining within the scope of the present disclosure.
- a second dielectric layer 48 is disposed over the resistive element layer 42 for thermal and electrical isolation. As shown, the second dielectric layer 48 is not disposed completely over the terminal pads 46 so that at least a portion of the terminal pads 46 remain exposed for connection to the lead wires 16 . More specifically, and as best shown in FIG. 6 b , the second dielectric layer 48 terminates around the recess 38 as shown such that the terminal pads 46 are exposed to the lead wires 16 for the electrical connection. In one form, the second dielectric layer 48 is created by a thermal spraying process and is generally a constant thickness. It should be understood that other processes and configurations (e.g., variable thickness and/or materials, among others) for the second dielectric layer 48 may be employed while remaining within the scope of the present disclosure.
- each of the dielectric layer 40 , resistive element layer 42 , terminal pads 46 , and second dielectric layer 48 are formed using a thermal spraying process, it should be understood that one or more of these layers may be formed by any number of processes, including, by way of example, those disclosed in copending U.S. application Ser. No. 10/752,359, titled “Combined Material Layering Technologies,” filed on Jan. 6, 2004, which is commonly assigned with the present application and the contents of which are incorporated herein by reference in their entirety.
- the protective cover 14 is disposed over the second dielectric layer 48 and is secured to the raised flanges 24 and 26 and the opposed chamfered surfaces 30 and 32 .
- the protective cover 14 in one form defines a cylindrical preform having a curved outer wall 52 and longitudinal flats 54 extending between end portions 56 and 58 .
- the protective cover 14 is a constant thickness foil material and is laser welded circumferentially around the raised flanges 24 and 26 of the substrate 12 and also laser welded longitudinally to the chamfered surfaces 30 and 32 along the slot 28 of the substrate 12 .
- the end portions 56 and 58 are laser welded to the raised flanges 24 and 26
- the longitudinal flats 54 are laser welded to the chamfered surfaces 30 and 32 . Accordingly, the layers disposed within the heater assembly 10 are protected from the outside environment, and more particularly from moisture intrusion, in part by the protective cover 14 .
- the protective cover 14 comprises an aperture 60 formed therethrough, wherein the aperture 60 disposed proximate the terminal pads 46 as more clearly shown in FIGS. 6 a and 6 b , and also in FIG. 2 .
- the aperture 60 provides access for securing the lead wires 16 to the terminal pads 46 , which is described in greater detail below.
- a lead cap assembly 18 is disposed around the pair of lead wires 16 and their insulation 17 and is secured to the protective cover 14 proximate the aperture 60 .
- the lead cap assembly 18 comprises a cap 64 , a pair of cap extensions 66 that are secured to the cap 64 , and a pair of sleeves 68 secured to the cap extensions 66 .
- an insulation disc 69 is disposed proximate the cap 64 as shown. The insulation disc 69 extends along the cap 64 between the exposed lead wires 16 and the lead cap assembly 18 and thus provides dielectric standoff between the lead wires 16 and the lead cap assembly 18 .
- the insulation disc 69 is a Mica material, however, other materials such as Aluminum Oxide or Steatite may also be employed while remaining within the scope of the present disclosure.
- the lead wires 16 and their insulation 17 thus extend through the pair of sleeves 68 , the cap extensions 66 , the cap 64 , and the insulation disc 69 , which is best shown in FIG. 6 b.
- the lead wires 16 are secured to the terminal pads 46 using an innovative termination spring 70 , which is illustrated in FIGS. 3 and 13 - 14 .
- the termination spring 70 comprises a first flexible arm 72 defining a proximal end portion 74 and a distal end portion 76 , and a second flexible arm 78 disposed opposite the first flexible arm 72 and similarly defining a proximal end portion 80 and a distal end portion 82 .
- a connecting member 84 extends between the proximal end portion 74 of the first flexible arm 72 and the proximal end portion 80 of the second flexible arm 78 .
- the distal end portion 76 of the first flexible arm 72 is disposed diagonally from the distal end portion 82 of the second flexible arm 78 .
- the distal end portions 76 and 82 define apertures 86 and 88 , respectively, through which the lead wires 16 extend and are secured.
- a positioning feature 85 may be provided (illustrated as a hole in this exemplary form) in order to position the termination spring 70 within the heater assembly 10 for attachment to the terminal pads 46 .
- the flexible arms 72 and 78 define an arcuate shape in one form of the present disclosure. As such, the flexible arms 72 and 78 are able to more smoothly transition load from the lead wires 16 to the terminal pads 46 , which shall be more fully understood with reference to the manufacturing methods as described in greater detail below.
- the termination spring 70 further comprises reduced areas 90 and 92 between the connecting member 84 and the flexible arms 72 and 78 . These reduced areas 90 and 92 are adapted for detachment such that the first flexible arm 72 can be separated from the second flexible arm 78 after the lead wires 16 are secured to the terminal pads 46 .
- the termination spring is a stainless steel material and is formed by a stamping process, however, other materials such as copper alloys, and other processes such as machining, may be employed while remaining within the scope of the present disclosure.
- the lead wires 16 are secured to the termination spring 70 through the apertures 86 and 88 , the lead wires 16 are passed through the insulation disc 69 and then the lead cap assembly 18 .
- the lead cap assembly 18 is then secured to the protective cover 14 around the aperture 60 as shown in FIGS. 1 and 2 .
- the aperture 60 defines a raised peripheral wall 94 , which provides additional space for securing the termination spring 70 and lead wires 16 to the terminal pads 46 within the heater assembly 10 .
- the lead cap assembly 18 is laser welded around the aperture 60 , however, other methods of securing the lead cap assembly 18 may be employed while remaining within the scope of the present disclosure, provided the aperture 60 is sealed closed from the outside environment.
- a secondary pair of lead wires 96 are secured to the lead wires 16 in one form of the present disclosure, wherein the secondary pair of lead wires 96 are formed of an insulating material that is not as heat resistant as the lead wires 16 , (yet the lead wires 96 are moisture resistant), such as Teflon® (polytetrafluoroethylene—PTFE) by way of example. Since the secondary pair of lead wires 96 are further away from the heater assembly 10 and thus the heat source, it is not necessary for these lead wires 96 to have the same level of heat resistance as the lead wires 16 and lead cap assembly 18 .
- Teflon® polytetrafluoroethylene—PTFE
- the lead wires 16 , lead cap assembly 18 , and the secondary pair of lead wires 96 should be moisture resistant such that moisture is inhibited from traveling to the heater assembly 10 , and more specifically the layers of the heater assembly 10 as previously illustrated and described.
- the secondary pair of lead wires 96 are secured to the lead wires 16 using a double-wall heat shrink tube 98 .
- the lead wires 16 and 96 are spliced together, and the heat shrink tube 98 is disposed around this interface.
- the heat shrink tube 98 in one form comprises a polytetrafluoroethylene (PTFE) outer wall 97 and a perfluoroalkoxy (PFA) inner wall 99 .
- PTFE polytetrafluoroethylene
- PFA perfluoroalkoxy
- the heater assembly 10 in one form further comprises tool supports 100 and 102 disposed along the slot 28 of the substrate 12 .
- the tool supports 100 and 102 are positioned along ledges 103 formed along the slot 28 of the substrate 12 as best shown in FIGS. 7 and 8 .
- the tool supports 100 and 102 are provided to accommodate an installation and removal tool such that the heater assembly 10 can be spread apart for installation and removal from the target object.
- at least one of the tool supports 100 defines a curved wall portion 104 to confine and guide a removal tool, such that as a removal tool is rotated within the space between the tool supports 100 and 102 , the heater assembly 10 may be more easily spread apart.
- a method of manufacturing the heater assembly 10 is now described in greater detail.
- a plurality of layers are formed onto the substrate 12 using a thermal spraying process, wherein a recessed area is formed on the layers.
- electrical terminations e.g., terminal pads 46
- the protective cover 14 is secured over the layers using a laser welding process, wherein edges of the protective cover 14 are welded circumferentially around raised end portions of the substrate 12 and welded longitudinally along the slot 28 of the substrate 12 .
- the pair of lead wires 16 are then secured to the termination spring 70 , preferably using a laser welding process, and then this assembly is secured to the terminal pads 46 using again, a laser welding process. More specifically, each proximal end portion 74 and 80 of the termination spring 70 is secured to the terminal pads 46 , and then the reduced areas 90 and 92 are severed. Accordingly, each of the flexible arms 72 and 78 are electrically separated.
- the lead wires 16 are then passed through the insulation disc 69 and the lead cap assembly 18 , and the lead cap assembly 18 is secured to the protective cover 14 proximate the aperture 60 , preferably by laser welding.
- the secondary pair of lead wires 96 are then secured to the lead wires 16 using the heat shrink tube 98 as previously set forth to complete the moisture resistant heater assembly 10 .
- the sleeves 68 of the lead cap assembly 18 are oriented approximately 45 degrees relative to the longitudinal axis of the substrate 12 .
- the lead wires 16 and 98 can be oriented longitudinally along the heater assembly 10 or laterally around the heater assembly 10 without each individual lead wire interfering with the other lead wire.
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- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Resistance Heating (AREA)
Abstract
A method of forming a layered heater assembly includes: forming a plurality of layers onto a substrate, the plurality of layers including a resistive element layer; forming electrical terminations in contact with the resistive element layer; securing a protective cover over the layers using a laser welding process, wherein edges of the protective cover are welded circumferentially around raised end portions of the substrate and welded longitudinally along a slotted portion of the substrate; securing a pair of lead wires to the electrical terminations; and securing a lead cap assembly around the pair of lead wires and to the protective cover using a laser welding process.
Description
- This application is a divisional of U.S. patent application Ser. No. 12/270,773, filed on Nov. 13, 2008, which claims the benefit of provisional application Ser. No. 60/988,712, filed on Nov. 16, 2007. The contents of these applications are incorporated herein by reference in their entirety.
- The present disclosure relates to resistance heaters, such as layered heaters by way of example, and more particularly to an apparatus and method for reducing moisture intrusion into such resistance heaters.
- The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
- Layered heaters are typically used in applications where space is limited, when heat output needs vary across a surface, where rapid thermal response is desirous, or in ultra-clean applications where moisture or other contaminants can migrate into conventional heaters. A layered heater generally comprises layers of different materials, namely, a dielectric and a resistive material, which are applied to a substrate. The dielectric material is applied first to the substrate and provides electrical isolation between the substrate and the electrically-live resistive material and also reduces current leakage to ground during operation. The resistive material is applied to the dielectric material in a predetermined pattern and provides a resistive heater circuit. The layered heater also includes leads that connect the resistive heater circuit to an electrical power source, which is typically cycled by a temperature controller. The lead-to-resistive circuit interface is also typically protected both mechanically and electrically from extraneous contact by providing strain relief and electrical isolation through a protective layer. Accordingly, layered heaters are highly customizable for a variety of heating applications.
- Layered heaters may be “thick” film, “thin” film, or “thermally sprayed,” among others, wherein the primary difference between these types of layered heaters is the method in which the layers are formed. For example, the layers for thick film heaters are typically formed using processes such as screen printing, decal application, or film dispensing heads, among others. The layers for thin film heaters are typically formed using deposition processes such as ion plating, sputtering, chemical vapor deposition (CVD), and physical vapor deposition (PVD), among others. Yet another series of processes distinct from thin and thick film techniques are those known as thermal spraying processes, which may include by way of example flame spraying, plasma spraying, wire arc spraying, and HVOF (High Velocity Oxygen Fuel), among others.
- Thermally sprayed layered heaters are generally formed by spraying molten powder or wire feedstock onto a substrate in the requisite layers as set forth above. The molten material impacts the substrate, or layers that have previously been applied over the substrate, resulting in lenticular or lamellar grain structure from the rapid solidification of small globules, flattened from striking a cooler surface at relatively high velocities. Due to this resultant grain structure, a common characteristic of thermally sprayed heaters is porosity, which can be beneficial in terms of fracture toughness, but also detrimental in terms of moisture absorption. In heater applications, if the thermally sprayed layers absorb an excessive amount of moisture, this moisture can cause the heater to fail during operation by mechanisms such as delaminating the individual layers or interrupting the supply of electrical power, or enabling excessive leakage current to ground.
- Moisture absorption is also an issue in many other types of resistance heaters, and thus improved devices and methods to counteract the adverse affects of moisture on heater performance are continually appreciated in the field of resistance heaters.
- In one form, a method of forming a heater assembly comprising: forming a plurality of layers onto a substrate using a thermal spray process, wherein a recessed area for a termination is disposed on the layers; forming electrical terminations proximate the recessed area; securing a protective cover over the layers using a laser welding process, wherein edges of the protective cover are welded circumferentially around raised end portions of the substrate and welded longitudinally along a slotted portion of the substrate; securing a pair of lead wires to the electrical terminations within the recessed area; and securing a lead cap assembly around the pair of lead wires and to the protective cover.
- In another form, a method of forming a layered heater assembly comprising: forming a plurality of layers onto a substrate, the plurality of layers including a resistive element layer; forming electrical terminations in contact with the resistive element layer; securing a protective cover over the layers using a laser welding process, wherein edges of the protective cover are welded circumferentially around raised end portions of the substrate and welded longitudinally along a slotted portion of the substrate; securing a pair of lead wires to the electrical terminations; securing a lead cap assembly around the pair of lead wires and to the protective cover using a laser welding process.
- In still another form, a method of forming a heater assembly comprising: preparing a substrate having an outer surface and a recessed area recessed from the outer surface; thermally spraying a resistive layer on the outer surface of the substrate; forming a pair of terminal pads in the recessed area and connecting the terminal pads to the resistive layer; and securing a protective layer to the substrate to protect the resistive layer and the terminal pads against moisture intrusion.
- Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
- The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.
-
FIG. 1 is a perspective view of a heater assembly constructed in accordance with the principles of the present disclosure; -
FIG. 2 is an enlarged perspective view of the heater assembly in accordance with the principles of the present disclosure; -
FIG. 3 is an exploded perspective view of the heater assembly in accordance with the principles of the present disclosure; -
FIG. 4 is a top view of the heater assembly in accordance with the principles of the present disclosure; -
FIG. 5 a is a longitudinal cross-sectional view, taken along line A-A ofFIG. 4 , illustrating an internal construction of the heater assembly in accordance with the principles of the present disclosure; -
FIG. 5 b is a detail view, within view B-B ofFIG. 5 a, illustrating various layers of the heater assembly and constructed in accordance with the principles of the present disclosure; -
FIG. 6 a is a cross-sectional view, taken along line C-C ofFIG. 4 , illustrating a termination area of the heater assembly and constructed in accordance with the principles of the present disclosure; -
FIG. 6 b is a detail view, within view D-D ofFIG. 6 a, illustrating the layers and terminal pads of the heater assembly and constructed in accordance with the principles of the present disclosure; -
FIG. 7 is a cross-sectional view, taken along line E-E ofFIG. 4 , illustrating the termination area and tool supports constructed in accordance with the principles of the present disclosure; -
FIG. 8 is a perspective view of a substrate constructed in accordance with the principles of the present disclosure; -
FIG. 9 is a top view of the substrate in accordance with the principles of the present disclosure; -
FIG. 10 is a perspective view of a protective cover constructed in accordance with the principles of the present disclosure; -
FIG. 11 is a perspective view of a lead cap assembly constructed in accordance with the principles of the present disclosure; -
FIG. 12 a is a perspective view of the heater assembly and a set of secondary lead wires constructed in accordance with the principles of the present disclosure; -
FIG. 12 b is a partial cross-sectional view of a connection between lead wires using a heat shrink tube and constructed in accordance with the principles of the present disclosure; -
FIG. 13 is a plan view of a termination spring constructed in accordance with the principles of the present disclosure; -
FIG. 14 is an enlarged perspective view of lead wires positioned for being secured to a termination spring and constructed in accordance with the principles of the present disclosure; and -
FIG. 15 is a flow diagram illustrating a method of manufacturing a heater assembly in accordance with the principles of the present disclosure. - The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. It should be understood that throughout the drawings, corresponding reference numerals indicate like or corresponding parts and features.
- Referring to
FIGS. 1-4 , a heater assembly in accordance with the principles of the present disclosure is illustrated and generally indicated byreference numeral 10. In one form, the heater assembly comprises asubstrate 12, a plurality of layers (not shown) disposed on the substrate that will be described in greater detail below, aprotective cover 14 disposed over the layers and secured to thesubstrate 12, a pair of lead wires 16 (surrounded by insulation 17) secured to theheater assembly 10, and alead cap assembly 18 disposed around the pair oflead wires 16 and secured to theprotective cover 14. Theheater assembly 10 is adapted for use around a target object to be heated such as a hot runner nozzle (not shown) by way of example, hence the geometrical configuration of a cylinder as shown. It should be understood that theheater assembly 10 may take other geometrical configurations such as flat, rectangular, or other polygonal shapes while remaining within the scope of the present disclosure. Additionally, although a layered heater construction is employed with theheater assembly 10 as illustrated and described herein, it should be understood that other types of heaters, such as resistive wire, resistive foil, or compacted ceramic, by way of example, may be employed while remaining within the scope of the present disclosure. - As shown in
FIG. 3 and more particularly inFIGS. 8 and 9 , one form of thesubstrate 12 is illustrated and now described in greater detail. In this form, thesubstrate 12 comprises opposedend portions flanges slot 28 extends between theopposed end portions chamfered surfaces slot 28 and across the raisedflanges substrate 12 defines a cylindrical configuration as shown and includes aninternal bore 34 that is adapted for placement around a heating target such as a hot runner nozzle, by way of example. Anouter surface 36 extends between the raisedflanges recess 38 is disposed on theouter surface 36. Therecess 38 accommodates a termination area as described in greater detail below. Thesubstrate 12 in one form is a stainless steel material, however, it should be understood that a variety of materials may be employed while remaining within the scope of the present disclosure. - Referring now to
FIGS. 4-6 , the plurality of layers are illustrated and now described in greater detail. The layers include, by way of example, afirst dielectric layer 40 disposed over thesubstrate 12 and in one form extending between the raisedflanges substrate 12. Thefirst dielectric layer 40 is also formed over therecess 38 on thesubstrate 12, and as such, takes on the form of therecess 38 as shown. In one form, thefirst dielectric layer 40 is formed using a thermal spraying process and is generally a constant thickness. It should be understood that other processes and configurations (e.g., variable thickness and/or materials, among others) for thefirst dielectric layer 40 may be employed while remaining within the scope of the present disclosure. - A
resistive element layer 42 is disposed over thefirst dielectric layer 40 and may take on the form of a resistive circuit 44 (shown dashed inFIG. 4 ) or may alternately be a continuous layer. In one form, theresistive element layer 42 is formed using a thermal spraying process and is generally a constant thickness. The pattern for theresistive circuit 44 may be formed by any number of methods and in one form is created by using a laser removal process such as that disclosed in copending U.S. application Ser. No. 10/872,752 titled “Method For the Production of an Electrically Conductive Resistive Layer and Heating and/or Cooling Device,” filed on Jun. 21, 2004, which is commonly assigned with the present application and the contents of which are incorporated herein by reference in their entirety. It should be understood that other processes and configurations (e.g., variable thickness and/or materials, among others) for theresistive element layer 42 may be employed while remaining within the scope of the present disclosure. Additionally, theresistive element layer 42 is also formed over therecess 38 on thesubstrate 12, and along with thefirst dielectric layer 40, takes on the form of therecess 38 as shown. - A pair of
terminal pads 46 are disposed over thefirst dielectric layer 40 and are in contact with theresistive element layer 42 as shown. Theterminal pads 46 are adapted for connecting thelead wires 16, which is described in greater detail below, for the application of electrical power to theheater assembly 10. In one form, theterminal pads 46 are created by a thermal spraying process, however, it should be understood that other processes may be employed while remaining within the scope of the present disclosure. - A
second dielectric layer 48 is disposed over theresistive element layer 42 for thermal and electrical isolation. As shown, thesecond dielectric layer 48 is not disposed completely over theterminal pads 46 so that at least a portion of theterminal pads 46 remain exposed for connection to thelead wires 16. More specifically, and as best shown inFIG. 6 b, thesecond dielectric layer 48 terminates around therecess 38 as shown such that theterminal pads 46 are exposed to thelead wires 16 for the electrical connection. In one form, thesecond dielectric layer 48 is created by a thermal spraying process and is generally a constant thickness. It should be understood that other processes and configurations (e.g., variable thickness and/or materials, among others) for thesecond dielectric layer 48 may be employed while remaining within the scope of the present disclosure. - While each of the
dielectric layer 40,resistive element layer 42,terminal pads 46, and seconddielectric layer 48 are formed using a thermal spraying process, it should be understood that one or more of these layers may be formed by any number of processes, including, by way of example, those disclosed in copending U.S. application Ser. No. 10/752,359, titled “Combined Material Layering Technologies,” filed on Jan. 6, 2004, which is commonly assigned with the present application and the contents of which are incorporated herein by reference in their entirety. - Referring now to
FIGS. 1-10 , theprotective cover 14 is disposed over thesecond dielectric layer 48 and is secured to the raisedflanges FIG. 10 , theprotective cover 14 in one form defines a cylindrical preform having a curvedouter wall 52 andlongitudinal flats 54 extending betweenend portions protective cover 14 is a constant thickness foil material and is laser welded circumferentially around the raisedflanges substrate 12 and also laser welded longitudinally to the chamfered surfaces 30 and 32 along theslot 28 of thesubstrate 12. More specifically, theend portions flanges longitudinal flats 54 are laser welded to the chamfered surfaces 30 and 32. Accordingly, the layers disposed within theheater assembly 10 are protected from the outside environment, and more particularly from moisture intrusion, in part by theprotective cover 14. - As further shown, the
protective cover 14 comprises anaperture 60 formed therethrough, wherein theaperture 60 disposed proximate theterminal pads 46 as more clearly shown inFIGS. 6 a and 6 b, and also inFIG. 2 . As such, theaperture 60 provides access for securing thelead wires 16 to theterminal pads 46, which is described in greater detail below. - Referring now to
FIGS. 1-3 , 6 a-6 b, and 11, alead cap assembly 18 is disposed around the pair oflead wires 16 and theirinsulation 17 and is secured to theprotective cover 14 proximate theaperture 60. In one form, thelead cap assembly 18 comprises acap 64, a pair ofcap extensions 66 that are secured to thecap 64, and a pair ofsleeves 68 secured to thecap extensions 66. Additionally, aninsulation disc 69 is disposed proximate thecap 64 as shown. Theinsulation disc 69 extends along thecap 64 between the exposedlead wires 16 and thelead cap assembly 18 and thus provides dielectric standoff between thelead wires 16 and thelead cap assembly 18. In one form, theinsulation disc 69 is a Mica material, however, other materials such as Aluminum Oxide or Steatite may also be employed while remaining within the scope of the present disclosure. Thelead wires 16 and theirinsulation 17 thus extend through the pair ofsleeves 68, thecap extensions 66, thecap 64, and theinsulation disc 69, which is best shown inFIG. 6 b. - In one form of the present disclosure, the
lead wires 16 are secured to theterminal pads 46 using aninnovative termination spring 70, which is illustrated in FIGS. 3 and 13-14. Thetermination spring 70 comprises a firstflexible arm 72 defining aproximal end portion 74 and adistal end portion 76, and a secondflexible arm 78 disposed opposite the firstflexible arm 72 and similarly defining aproximal end portion 80 and adistal end portion 82. A connectingmember 84 extends between theproximal end portion 74 of the firstflexible arm 72 and theproximal end portion 80 of the secondflexible arm 78. Further, thedistal end portion 76 of the firstflexible arm 72 is disposed diagonally from thedistal end portion 82 of the secondflexible arm 78. In one form, thedistal end portions apertures lead wires 16 extend and are secured. Additionally, apositioning feature 85 may be provided (illustrated as a hole in this exemplary form) in order to position thetermination spring 70 within theheater assembly 10 for attachment to theterminal pads 46. - As further shown, the
flexible arms flexible arms lead wires 16 to theterminal pads 46, which shall be more fully understood with reference to the manufacturing methods as described in greater detail below. Thetermination spring 70 further comprises reducedareas member 84 and theflexible arms areas flexible arm 72 can be separated from the secondflexible arm 78 after thelead wires 16 are secured to theterminal pads 46. Preferably, the termination spring is a stainless steel material and is formed by a stamping process, however, other materials such as copper alloys, and other processes such as machining, may be employed while remaining within the scope of the present disclosure. - After the
lead wires 16 are secured to thetermination spring 70 through theapertures lead wires 16 are passed through theinsulation disc 69 and then thelead cap assembly 18. Thelead cap assembly 18 is then secured to theprotective cover 14 around theaperture 60 as shown inFIGS. 1 and 2 . In one form, theaperture 60 defines a raisedperipheral wall 94, which provides additional space for securing thetermination spring 70 andlead wires 16 to theterminal pads 46 within theheater assembly 10. Preferably, thelead cap assembly 18 is laser welded around theaperture 60, however, other methods of securing thelead cap assembly 18 may be employed while remaining within the scope of the present disclosure, provided theaperture 60 is sealed closed from the outside environment. - Referring to
FIGS. 12 a and 12 b, a secondary pair oflead wires 96 are secured to thelead wires 16 in one form of the present disclosure, wherein the secondary pair oflead wires 96 are formed of an insulating material that is not as heat resistant as thelead wires 16, (yet thelead wires 96 are moisture resistant), such as Teflon® (polytetrafluoroethylene—PTFE) by way of example. Since the secondary pair oflead wires 96 are further away from theheater assembly 10 and thus the heat source, it is not necessary for theselead wires 96 to have the same level of heat resistance as thelead wires 16 andlead cap assembly 18. However, thelead wires 16,lead cap assembly 18, and the secondary pair oflead wires 96 should be moisture resistant such that moisture is inhibited from traveling to theheater assembly 10, and more specifically the layers of theheater assembly 10 as previously illustrated and described. Accordingly, in one form, the secondary pair oflead wires 96 are secured to thelead wires 16 using a double-wall heat shrinktube 98. As best shown in FIG. 12 b, thelead wires tube 98 is disposed around this interface. Theheat shrink tube 98 in one form comprises a polytetrafluoroethylene (PTFE)outer wall 97 and a perfluoroalkoxy (PFA)inner wall 99. With theouter wall 97 andinner wall 99, and the heat sealing nature of the heat shrinktube 98, the connection between thelead wires 16 and thesecondary lead wires 96 is advantageously resistant to moisture. - Referring now to
FIGS. 1-3 and 7, theheater assembly 10 in one form further comprises tool supports 100 and 102 disposed along theslot 28 of thesubstrate 12. In one form, the tool supports 100 and 102 are positioned alongledges 103 formed along theslot 28 of thesubstrate 12 as best shown inFIGS. 7 and 8 . Generally, the tool supports 100 and 102 are provided to accommodate an installation and removal tool such that theheater assembly 10 can be spread apart for installation and removal from the target object. As shown, at least one of the tool supports 100 defines acurved wall portion 104 to confine and guide a removal tool, such that as a removal tool is rotated within the space between the tool supports 100 and 102, theheater assembly 10 may be more easily spread apart. This general concept is illustrated and described in greater detail in copending U.S. application Ser. No. 11/602,707, titled “Split-Sleeve Heater and Removal Tool,” filed on Nov. 21, 2006, which is commonly assigned with the present application and the contents of which are incorporated by reference herein in their entirety. It should be understood that theheater assembly 10 may be provided with or without the tool supports 100 and 102 while still remaining within the scope of the present disclosure. - Referring now to
FIG. 15 , a method of manufacturing theheater assembly 10 is now described in greater detail. First, a plurality of layers (as previously set forth) are formed onto thesubstrate 12 using a thermal spraying process, wherein a recessed area is formed on the layers. Next, electrical terminations (e.g., terminal pads 46) are formed proximate the recessed area, preferably using a thermal spraying process. Theprotective cover 14 is secured over the layers using a laser welding process, wherein edges of theprotective cover 14 are welded circumferentially around raised end portions of thesubstrate 12 and welded longitudinally along theslot 28 of thesubstrate 12. The pair oflead wires 16 are then secured to thetermination spring 70, preferably using a laser welding process, and then this assembly is secured to theterminal pads 46 using again, a laser welding process. More specifically, eachproximal end portion termination spring 70 is secured to theterminal pads 46, and then the reducedareas flexible arms lead wires 16 are then passed through theinsulation disc 69 and thelead cap assembly 18, and thelead cap assembly 18 is secured to theprotective cover 14 proximate theaperture 60, preferably by laser welding. The secondary pair oflead wires 96 are then secured to thelead wires 16 using the heat shrinktube 98 as previously set forth to complete the moistureresistant heater assembly 10. - Preferably, as shown in
FIGS. 1 and 2 , thesleeves 68 of thelead cap assembly 18 are oriented approximately 45 degrees relative to the longitudinal axis of thesubstrate 12. By orienting thesleeves 68 in this fashion, thelead wires heater assembly 10 or laterally around theheater assembly 10 without each individual lead wire interfering with the other lead wire. - The present disclosure is merely exemplary in nature and, thus, variations that do not depart from the gist of the disclosure are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention.
Claims (20)
1. A method of forming a heater assembly comprising:
forming a plurality of layers onto a substrate using a thermal spray process, wherein a recessed area for a termination is disposed on the layers;
forming electrical terminations proximate the recessed area;
securing a protective cover over the layers using a laser welding process, wherein edges of the protective cover are welded circumferentially around raised end portions of the substrate and welded longitudinally along a slotted portion of the substrate;
securing a pair of lead wires to the electrical terminations within the recessed area; and
securing a lead cap assembly around the pair of lead wires and to the protective cover.
2. The method according to claim 1 , wherein the plurality of layers includes a resistive element layer that is formed by a laser removal process.
3. The method according to claim 1 , wherein the lead wires are secured to the electrical terminations using a laser welding process.
4. The method according to claim 1 , wherein the lead cap assembly is secured to the protective cover using a laser welding process.
5. The method according to claim 1 , wherein the lead wires are secured to the electrical terminations with a termination spring, and the termination spring is severed after the termination spring is secured to the electrical terminations.
6. A method of forming a layered heater assembly comprising:
forming a plurality of layers onto a substrate, the plurality of layers including a resistive element layer;
forming electrical terminations in contact with the resistive element layer;
securing a protective cover over the layers using a laser welding process, wherein edges of the protective cover are welded circumferentially around raised end portions of the substrate and welded longitudinally along a slotted portion of the substrate;
securing a pair of lead wires to the electrical terminations; and
securing a lead cap assembly around the pair of lead wires and to the protective cover using a laser welding process.
7. The method according to claim 6 , wherein the plurality of layers are formed by a thermal spray process.
8. The method according to claim 6 further comprising forming a recessed area for the electrical terminations.
9. The method according to claim 6 , wherein the resistive element layer is formed by a laser removal process.
10. The method according to claim 6 , wherein the lead wires are secured to the electrical terminations with a termination spring, and a portion of the termination spring is severed after the termination spring is secured to the electrical terminations.
11. A method of forming a heater assembly comprising:
preparing a substrate having an outer surface and a recessed area recessed from the outer surface;
thermally spraying a resistive layer on the outer surface of the substrate;
forming a pair of terminal pads in the recessed area and connecting the terminal pads to the resistive layer; and
securing a protective layer to the substrate to protect the resistive layer and the terminal pads against moisture intrusion.
12. The method according to claim 11 , wherein the protective layer defines an aperture.
13. The method according to claim 12 , further comprising aligning the aperture with the terminal pads.
14. The method according to claim 12 , further comprising inserting a pair of leads wires through the aperture to connect the pair of lead wires to the terminal pads.
15. The method according to claim 14 , further comprising securing a pair of lead wires to a termination spring.
16. The method according to claim 15 , further comprising placing the termination spring in the recessed area to connect the termination spring to the terminal pads.
17. The method according to claim 16 , further comprising severing the termination spring into at least two pieces so that the terminal pads are electrically disconnected.
18. The method according to claim 14 , further comprising inserting the lead wires through a lead cap assembly.
19. The method according to claim 18 , further comprising securing the lead cap assembly to the protective layer.
20. The method according to claim 18 , further comprising laser-welding the lead cap assembly to the protective layer.
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US14/728,515 US10361019B2 (en) | 2007-11-16 | 2015-06-02 | Moisture resistant layered sleeve heater and method of manufacture thereof |
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US12/270,773 US8395092B2 (en) | 2007-11-16 | 2008-11-13 | Moisture resistant layered sleeve heater and method of manufacturing thereof |
US13/762,842 US20130152383A1 (en) | 2007-11-16 | 2013-02-08 | Moisture resistant layered sleeve heater and method of manufacture thereof |
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US13/762,871 Active 2030-10-05 US10236103B2 (en) | 2007-11-16 | 2013-02-08 | Moisture resistant layered sleeve heater and method of manufacture thereof |
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US14/728,515 Active 2030-08-10 US10361019B2 (en) | 2007-11-16 | 2015-06-02 | Moisture resistant layered sleeve heater and method of manufacture thereof |
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WO2011137266A1 (en) * | 2010-04-28 | 2011-11-03 | Watlow Electric Manufacturing Company | Flow through heater |
DE102010061271A1 (en) * | 2010-12-15 | 2012-06-21 | Contitech Schlauch Gmbh | Heatable connection device for media-carrying, electrically heatable hoses |
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CN108890156A (en) * | 2018-07-04 | 2018-11-27 | 潘真清 | A kind of laser welding repairs the device of torsion cylinder |
KR20210134415A (en) * | 2019-03-28 | 2021-11-09 | 엠케이에스 인스트루먼츠 인코포레이티드 | Low Profile Heater Apparatus and Manufacturing Method |
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KR102551053B1 (en) * | 2021-05-12 | 2023-07-05 | 주식회사 한국제이텍트써모시스템 | Heater unit of heat treatment oven |
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- 2008-11-13 CA CA2719410A patent/CA2719410C/en not_active Expired - Fee Related
- 2008-11-13 JP JP2010534161A patent/JP5238038B2/en not_active Expired - Fee Related
- 2008-11-13 WO PCT/US2008/083376 patent/WO2009064862A1/en active Application Filing
- 2008-11-13 US US12/270,773 patent/US8395092B2/en active Active
- 2008-11-13 EP EP08850847.8A patent/EP2215889B1/en not_active Not-in-force
- 2008-11-13 MX MX2010005410A patent/MX2010005410A/en active IP Right Grant
- 2008-11-14 TW TW097144127A patent/TW200936973A/en unknown
-
2013
- 2013-02-08 US US13/762,842 patent/US20130152383A1/en not_active Abandoned
- 2013-02-08 US US13/762,871 patent/US10236103B2/en active Active
-
2015
- 2015-06-02 US US14/728,515 patent/US10361019B2/en active Active
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Also Published As
Publication number | Publication date |
---|---|
EP2215889A1 (en) | 2010-08-11 |
US20150262739A1 (en) | 2015-09-17 |
JP5238038B2 (en) | 2013-07-17 |
US20090127244A1 (en) | 2009-05-21 |
US8395092B2 (en) | 2013-03-12 |
TW200936973A (en) | 2009-09-01 |
CN101911828A (en) | 2010-12-08 |
US20130146584A1 (en) | 2013-06-13 |
MX2010005410A (en) | 2010-06-23 |
EP2215889B1 (en) | 2016-04-13 |
CA2719410C (en) | 2016-09-06 |
US10361019B2 (en) | 2019-07-23 |
CN101911828B (en) | 2014-02-26 |
CA2719410A1 (en) | 2009-05-22 |
JP2011503826A (en) | 2011-01-27 |
US10236103B2 (en) | 2019-03-19 |
WO2009064862A1 (en) | 2009-05-22 |
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