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WO1997034720A1 - Materiau composite et son procede de fabrication - Google Patents

Materiau composite et son procede de fabrication Download PDF

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Publication number
WO1997034720A1
WO1997034720A1 PCT/DE1997/000482 DE9700482W WO9734720A1 WO 1997034720 A1 WO1997034720 A1 WO 1997034720A1 DE 9700482 W DE9700482 W DE 9700482W WO 9734720 A1 WO9734720 A1 WO 9734720A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite material
phase
material according
mpa
binding metal
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.)
Ceased
Application number
PCT/DE1997/000482
Other languages
German (de)
English (en)
Inventor
Klaus RÖDIGER
Klaus Dreyer
Helmut Holzhauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Widia GmbH
Original Assignee
Widia GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Widia GmbH filed Critical Widia GmbH
Publication of WO1997034720A1 publication Critical patent/WO1997034720A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/22—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/24—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/004—Article comprising helical form elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • B22F2005/103—Cavity made by removal of insert
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to composite materials, consisting essentially of a cermet material with a binder metal phase of
  • the rest of the binder metal phase a powder metallurgy steel or a metallic or ceramic magnetic material.
  • the invention further relates to a method for producing this composite material.
  • the starting powders are mixed, homogenized and ground in accordance with the desired quantitative composition before they are subjected to a shaping for producing a green body, which is then sintered.
  • the following variants of the shaping method are known from the prior art:
  • the compacted blank is shaped to the desired geometry in the green state or after its pre-sintering by means of mechanical turning, cutting, drilling and grinding operations.
  • the mixed and ground starting powder is granulated and compressed with the aid of plastic binders by means of die presses to the desired final shape.
  • the starting powder mixture is made flowable by adding a thermoplastic plastic binder and injection molded under high pressure in accordance with the injection molding process known for plastics.
  • the necessary injection molding tools increase the manufacturing costs considerably.
  • to remove the introduced Binder's process steps are necessary in which gaseous nitric acid or organic solvents are used, the handling and disposal of which, from an environmental point of view, is further cost-increasing.
  • Strand-shaped blanks can be formed using plasticizers such as wax using screw or piston extrusion presses.
  • the qualitative and quantitative composition of the composite materials consisting of a cermet material, a hard metal or a powder-metallurgy steel is basically known in the prior art, for example from DE 43 40 652 A1.
  • the respective base materials, namely cermets, hard metals or steels can be in pure form or have additives of various types, namely metals, further hard materials, ceramic materials and single-crystal reinforcing materials in whisker or plate form.
  • the fundamental difference between the composite materials claimed is that the starting materials are shaped into a non-porous green body by hot casting prior to sintering. Hot casting is basically for the production of ceramic moldings from cfi / Ber. DKG 72 (1995) No. 10, pages 640 to 642.
  • the hot casting process which is also referred to as low-pressure hot spraying or low-pressure injection molding, is based on the fact that the powdery starting mixtures are brought into a flowable state by adding a thermoplastic binder, essentially paraffins and / or liquid-melting waxes and surface-active substances - including surfactants or called detergents - are added.
  • the surfactants serve as a connection between the solid particles, which they coat "in one layer" and the waxes and / or paraffins.
  • cermet, hard metal or steel powder contain components that have much higher densities up to 16 g / cm 3 .
  • hot casting can also be used to shape the composite materials characterized in claim 1.
  • the hot casting of the suspension consisting of the powdery starting materials and the thermoplastic binder enables the production of molded parts with a high degree of complexity, so undercuts, transverse bores and blind holes, large wall thickness differences, threads, grooves, surface structures, lettering and combinations of the aforementioned shapes can be cost-effectively , in particular by approximately 80% to 90% lower tool costs compared to high-pressure injection molding.
  • Application products are, in particular, indexable inserts with complex chip form geometries, milling cutter blanks with a twisted chip chamber, rotor milling cutters, screws, micro-drills, drills and cutting inserts with flushing holes, guide fingers for cigarette manufacture, rotors, pump parts, such as bearing rings, shaft seals and shafts, gear wheels, complex nozzles, bearing shells, Watch case, scissors blanks, Cylinders for metering pumps, control pistons for paint spray guns, balls, work and transport rollers for the packaging industry, paddle wheels and the like.
  • the hot casting process according to the invention of cermet, hard metal, steel and / or metallic or ceramic magnet materials is characterized in accordance with claim 17, that the components of the composite materials in the desired quantitative mixing ratio as powdery starting materials after grinding with a thermoplastic binder, the proportion of which in the total amount is 20 to 50% by volume, preferably 30 to 40% by volume, and which has a viscosity between 3 to 6 mPa s, in a stable dispersive suspension with a viscosity between 100 mPa s and 5 Pa s is transferred, this suspension is cast into a shape corresponding to the desired contours of the composite component to be produced without pressure or under a pressure of at most 5 MPa, preferably 0.1 to 1 MPa, at 70 ° C.
  • thermoplastic binder to 120 ° C. and at temperatures, which are above the evaporation temperatures of the thermoplastic binder, is heated and the thermoplastic B in which the stripped body is sintered.
  • the powder starting mixture and the thermoplastic binder by hot casting, i.e., above the melting temperature of the thermoplastic binder, has the true-to-shape negative contour of the finished component to be manufactured, taking into account the sintering shrinkage.
  • the low pressures used do not place as high demands on the mold as in high-pressure injection molding. In particular, less expensive materials can be used as mold material.
  • the average grain size of the powdered raw materials is less than 15 ⁇ m (for steel and magnetic Substances below 100 ⁇ m), it can be in particular ⁇ 3 p and / or the viscosity of the suspension is between 100 mPa s and 2000 mPa s. Variations in the average grain size are included insofar as, for example, some of the powdered starting materials can have a coarser grain and the rest can have a finer grain.
  • the thermoplastic binder consists of waxes and / or paraffins, to which 2 to 30% by volume of surface-active substances, preferably with an aliphatic hydrocarbon residue or alkylbenzene residue with 10 to 22 C atoms, are added.
  • surface-active substances preferably with an aliphatic hydrocarbon residue or alkylbenzene residue with 10 to 22 C atoms.
  • the suspension is preferably cast in casting molds made of brass, copper, steel or plastic.
  • the thermoplastic binder can be driven out in stages, namely in a first stage at temperatures up to 300 ° C. at which 50 to 80% by volume of the thermoplastic binder is expelled. be driven.
  • the residual content of the thermoplastic binder remaining in the hot-cast molded body can then be used in the course of further treatment with a view to greater strength of the blank.
  • the rest of the thermoplastic binder is then expelled at higher temperatures.
  • the thermoplastic binder is preferably expelled in a protective gas atmosphere, as a result of which undesired reactions of the green body with the furnace atmosphere can be avoided.
  • the shaped body in the first stage, can be coated with an absorbent material (a powder bed), such as Al 2 O 3 powder, or lie on a ceramic base, in particular A1 2 0 3 , and the second stage can be carried out in a sintering furnace.
  • a powder bed such as Al 2 O 3 powder
  • the powder bed and the ceramic underlay serve as an aid for sucking up the liquefied binder.
  • the residual content of thermoplastic binder in the molded body is preferably 20 to 30% by volume before being transferred to the sintering furnace, this residual content ensuring adequate stabilization of the molded body.
  • the two-stage binder removal can optionally also be exploited to that targeted in the first stage at temperatures up to 300 * C acids present as surface-active substances, such as oleic acid, stearic acid, etc., are cracked, and the resulting cracking carbon for carburizing of Shaped body are used.
  • C acids present as surface-active substances such as oleic acid, stearic acid, etc.
  • the hot casting according to the invention is not only limited to the production of moldings of homogeneous composition. Inhomogeneities in the form of changing substance compositions can be achieved by casting molds with two different pouring channels, into which suspensions of different compositions are poured. In particular, different compositions can be cast on top of one another or next to one another, which merge into one another at the respective interfaces and also make it possible to set radial composition gradients if the cast core material is encapsulated by a material of a different composition.
  • a core can first be produced in a first mold by hot or injection molding, which is then transferred to a second mold and encased in a shell made of hot-moldable material.
  • abrasion-resistant wear protection layers can preferably be cast around a tough core, wherein the wear protection layers can consist of one or more layers of the same or different material composition.
  • a strand of plastic preferably polyethylene or wax or another material that can be melted out at the sintering temperature, is firmly adhered as a placeholder for a later channel and that the molded body consisting of the strand and the core is then extrusion-coated in a casting mold by hot casting and the one thus produced Composite body is sintered, the strand thermally decomposing.
  • the strand can be formed in a linear form, for example in the case of piercing tools, or in a spiral form in the case of drill blanks.
  • a hard material powder mixture of 94% by mass of WC and 6% by mass of Co is mixed, ground and then with a thermoplastic binder, which is 45% by volume based on the total mixture, to give a 75 ° C. warm suspension been melted.
  • 70% by volume of the thermoplastic binder consisted of a low-chain paraffin, 20% by volume of wax and 10% by volume of oleic acid.
  • the hot slip suspension has a viscosity that is greater than 100 mPas. If smaller viscosity values were reached, powdery WC / Co was refilled in an amount until the desired minimum viscosity was reached and the dispersion was stable.
  • the slip is put into a casting mold without pressure or at a maximum of 1 MPa via sprue channels, the inner contours of which correspond to the molded component to be produced, taking into account the sintering shrinkage.
  • the casting mold is then cooled to room temperature, the molding is removed and under protective gas in a powder bed up to 300 ° C. heated, except for a residual content of thermoplastic binder between 20 and 30% of the binder is driven off.
  • the molded body is placed on a graphite base in a sintering furnace and sintered at approx. 1450'C. In the warm-up phase up to 500 ° C, the residual binder is driven out into the gas phase.
  • thermoplastic binder consisted of 70% by volume of a low-chain paraffin, 24% by volume of wax and 6% by volume of stearic acid.
  • the thermoplastic binder was heated to 80 ° C. in a heatable mixing device and 2/3 of the powder mixture was added and mixed until the viscosity of the suspension decreased. The rest of the powder is then added and again mixed intensively.
  • the suspension has a viscosity above 100 mPas.
  • the slip thus produced is poured into a mold for a coil core under a pressure of 1 MPa and cooled. After cooling, the green compact is removed removed from the divisible casting mold and thermally debindered in an alumina powder bed in a push-through furnace under a hydrogen stream and sintered at 1350 ° C. for 4 hours.
  • cermets and powder-metallurgical steel starting grades of the type mentioned have been processed.
  • the starting grain sizes of the powder metallurgical materials were either on average below 1 ⁇ m (so-called fine grain). or below 2 ⁇ m.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Power Engineering (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne des matériaux composites qui comprennent principalement: un cermet comportant une phase métallique de liaison de 3 à 30 % en masse, avec un reste formé d'au moins une phase carbonitrure; ou un métal dur comportant au moins une phase solide dure de 65 à 99 %, avec un reste formé d'un résidu de phase de métal de liaison; ou un acier produit par métallurgie des poudres; ou un matériau magnétique métallique ou céramique. L'invention concerne également un procédé permettant de fabriquer ce matériau composite. Pour résoudre le problème consistant à trouver des matériaux composites et un procédé de fabrication qui permette de produire des matériaux composites peu coûteux sous la forme de pièces moulées de géométrie complexe et avec une rugosité de surface la plus réduite possible, il est proposé de fabriquer ledit matériau par moulage à chaud suivi de frittage. Pour cela, on transforme, à l'aide d'un liant thermoplastique, les produits de départ pulvérulents en une suspension dispersive stable ayant une viscosité comprise entre 100 mPa et 5 Pa, on coule cette suspension sans pression ou sous une pression maximale de 5 MPa, à une température comprise entre 70 et 120 °C, puis on la chauffe, le liant thermoplastique étant expulsé avant le frittage du corps devenu exempt de liant.
PCT/DE1997/000482 1996-03-16 1997-03-10 Materiau composite et son procede de fabrication Ceased WO1997034720A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19610410 1996-03-16
DE19610410.6 1996-03-16
DE19613309.2 1996-04-03
DE19613309 1996-04-03

Publications (1)

Publication Number Publication Date
WO1997034720A1 true WO1997034720A1 (fr) 1997-09-25

Family

ID=26023863

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1997/000482 Ceased WO1997034720A1 (fr) 1996-03-16 1997-03-10 Materiau composite et son procede de fabrication

Country Status (2)

Country Link
DE (1) DE19709651A1 (fr)
WO (1) WO1997034720A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12357061B2 (en) * 2021-12-23 2025-07-15 Eta Sa Manufacture Horlogère Suisse Portable object comprising a middle devoid of fastening horns and a removable bracelet

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK1306148T3 (da) * 2001-10-29 2007-01-29 Ceratizit Luxembourg Sarl Fremgangsmåde til gelstöbning af emner ud fra keramik-, glas- eller metalpulver
US7247186B1 (en) * 2003-05-20 2007-07-24 Exxonmobil Research And Engineering Company Advanced erosion resistant carbonitride cermets
CN100415919C (zh) * 2003-05-20 2008-09-03 埃克森美孚研究工程公司 高级抗侵蚀碳氮化物金属陶瓷
GB2429980A (en) * 2005-09-08 2007-03-14 John James Saveker Material comprising a carbide, boride or oxide and tungsten carbide
CN101641174B (zh) * 2007-03-21 2011-07-13 霍加纳斯股份有限公司 粉末金属聚合物复合材料
ATE522726T1 (de) 2008-07-10 2011-09-15 Grundfos Management As Strömungsführendes bauteil einer pumpe
DE102012213263A1 (de) 2011-09-20 2013-03-21 Robert Bosch Gmbh Handwerkzeugvorrichtung mit zumindest einer Ladespule

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1533035B1 (de) * 1965-06-17 1971-04-01 Tavkoezlesi Ki Verfahren zur pulvermetallurgischen herstellung von sinter teilen aus metall und oder metalloxidpulver mittels pasten guss
DE2422425A1 (de) * 1973-05-09 1974-11-28 Mallory & Co Inc P R Verfahren und vorrichtung zur herstellung von gegenstaenden
US4948426A (en) * 1989-10-17 1990-08-14 Sumitomo Metal Mining Company Limited Sintering metal powder and a process for making a sintered metal product
EP0443048A1 (fr) * 1989-09-14 1991-08-28 Sumitomo Electric Industries Ltd Procede de production de carbure cemente ou d'alliage de cermet
EP0516165A2 (fr) * 1991-05-31 1992-12-02 Sumitomo Electric Industries, Limited Procede pour la production d'un corps dur fritte
EP0576282A2 (fr) * 1992-06-24 1993-12-29 Sumitomo Special Metals Co., Ltd. Procédé de préparation d'aimants frittés du type R-Fe-B utilisant moulage pour injection
US5401292A (en) * 1992-08-03 1995-03-28 Isp Investments Inc. Carbonyl iron power premix composition
DE4332971A1 (de) * 1993-09-28 1995-03-30 Fischer Artur Werke Gmbh Verfahren zur Herstellung von ineinandergreifenden Teilen

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1533035B1 (de) * 1965-06-17 1971-04-01 Tavkoezlesi Ki Verfahren zur pulvermetallurgischen herstellung von sinter teilen aus metall und oder metalloxidpulver mittels pasten guss
DE2422425A1 (de) * 1973-05-09 1974-11-28 Mallory & Co Inc P R Verfahren und vorrichtung zur herstellung von gegenstaenden
EP0443048A1 (fr) * 1989-09-14 1991-08-28 Sumitomo Electric Industries Ltd Procede de production de carbure cemente ou d'alliage de cermet
US4948426A (en) * 1989-10-17 1990-08-14 Sumitomo Metal Mining Company Limited Sintering metal powder and a process for making a sintered metal product
EP0516165A2 (fr) * 1991-05-31 1992-12-02 Sumitomo Electric Industries, Limited Procede pour la production d'un corps dur fritte
EP0576282A2 (fr) * 1992-06-24 1993-12-29 Sumitomo Special Metals Co., Ltd. Procédé de préparation d'aimants frittés du type R-Fe-B utilisant moulage pour injection
US5401292A (en) * 1992-08-03 1995-03-28 Isp Investments Inc. Carbonyl iron power premix composition
DE4332971A1 (de) * 1993-09-28 1995-03-30 Fischer Artur Werke Gmbh Verfahren zur Herstellung von ineinandergreifenden Teilen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12357061B2 (en) * 2021-12-23 2025-07-15 Eta Sa Manufacture Horlogère Suisse Portable object comprising a middle devoid of fastening horns and a removable bracelet

Also Published As

Publication number Publication date
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