WO1994024613A1 - Vehicule compose de ferrite et de lithium - Google Patents

Vehicule compose de ferrite et de lithium Download PDF

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Publication number
WO1994024613A1
WO1994024613A1 PCT/US1994/003843 US9403843W WO9424613A1 WO 1994024613 A1 WO1994024613 A1 WO 1994024613A1 US 9403843 W US9403843 W US 9403843W WO 9424613 A1 WO9424613 A1 WO 9424613A1
Authority
WO
WIPO (PCT)
Prior art keywords
carrier
ferrite
lithium
lithium ferrite
carriers
Prior art date
Application number
PCT/US1994/003843
Other languages
English (en)
Other versions
WO1994024613B1 (fr
Inventor
Alan Sukovich
William R. Hutcheson
Original Assignee
Powdertech Corportion
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 Powdertech Corportion filed Critical Powdertech Corportion
Priority to EP94913384A priority Critical patent/EP0693191B1/fr
Priority to KR1019950704403A priority patent/KR960702123A/ko
Priority to DE69419742T priority patent/DE69419742T2/de
Priority to JP52331594A priority patent/JP3429312B2/ja
Publication of WO1994024613A1 publication Critical patent/WO1994024613A1/fr
Publication of WO1994024613B1 publication Critical patent/WO1994024613B1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/107—Developers with toner particles characterised by carrier particles having magnetic components
    • G03G9/1075—Structural characteristics of the carrier particles, e.g. shape or crystallographic structure
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/107—Developers with toner particles characterised by carrier particles having magnetic components
    • G03G9/108—Ferrite carrier, e.g. magnetite
    • G03G9/1085—Ferrite carrier, e.g. magnetite with non-ferrous metal oxide, e.g. MgO-Fe2O3

Definitions

  • the present invention relates to a magnetic carrier for use with electrophotographic development equipment and, more particularly, to an environmentally benign lithium ferrite carrier having a non-stoichiometric composition.
  • Carriers in the form of powder are used to transfer toner particles in electrophotographic development equipment, for example, in photocopying machines and most recently in laser printers.
  • such carriers are ferrites or ferrite powders in combination with various metals, for example, nickel, zinc, or copper.
  • the present invention comprises a carrier for electro ⁇ photographic developing comprising a generally non-stoichiometric lithium ferrite powder having a particular compositional range.
  • the carrier has a substantially spinel crystalline structure and may be formed in a generally spherical shaped magnetic core configuration for use in pre-existing conventional electrophotographic equipment.
  • Yet another object of the invention is to provide an electrophotographic carrier which is a non-stoichiometric lithium ferrite compound.
  • a further object of the invention is to provide a lithium ferrite powder for use as a carrier having a form and being in a condition for use with electrophotographic equipment already in service.
  • Another object of the invention is to provide an electrophotographic development carrier comprised of lithium ferrites having a range of composition.
  • Yet a further object of the invention is to provide a method for manufacture of a lithium ferrite carrier having a spinel crystalline structure and which is useful in electro- photographic processes.
  • FIGURE 1 is a phase diagram for lithium ferrite compositions illustrating the range of the composition of the carrier of the present invention
  • FIGURE 2 is a photomicrograph of the carrier of Example No. 1 of the invention at 50 magnification
  • FIGURE 3 is a photomicrograph of the carrier of Example No. 1 of the invention at 200 magnification
  • FIGURE 4 is a photomicrograph of the carrier of Example No. 2 of the invention at 50 magnification
  • FIGURE 5 is a photomicrograph of the carrier of Example No. 2 of the invention at 200 magnification
  • FIGURE 6 is a photomicrograph of the carrier of Example No. 3 of the invention at 50 magnification
  • FIGURE 7 is a photomicrograph of the carrier of Example No. 3 of the invention at 200 magnification
  • FIGURE 8 is a photomicrograph of the carrier of Example No. 4 of the invention at 50 magnification
  • FIGURE 9 is a photomicrograph of the carrier of Example No. 4 of the invention at 200 magnification
  • FIGURE 10 is a photomicrograph of the carrier of Example No. 5 of the invention at 50 magnification.
  • FIGURE 1 1 is a photomicrograph of the carrier of Example No. 5 of the invention at 200 magnification.
  • the present invention comprises a generally spherical shaped, magnetic carrier core powder which may be used for magnetic brush development in copy machines and laser printers.
  • magnetic carriers such as ferrites are used to transfer toner particles from a developer mix onto a photoreceptor. The particles are then transferred by the photoreceptor onto plain paper.
  • the ferrite carrier powders are typically in the form of spherical beads or powder which may or may not be coated with resin. Also typically the ferrites are combined with various metal oxides which enhance the utility of the carrier powder.
  • the present invention is a magnetic ferrite carrier powder which does not contain elements considered potentially hazardous such as nickel, copper, zinc and barium.
  • the present invention comprises a generally non-stoichiometric lithium ferrite.
  • Stoichiometric lithium ferrite composition may be represented by the following formulation:
  • Lithium is monovalent and thus requires an equal molar amount of trivalent iron to obtain the desired spinel crystalline structure as a ferrite. Consequently, the formulas set forth above represent the stoichiometric composition of lithium ferrite.
  • compositional range which is preferred or which is specified as comprising the present invention is represented by the following generally non- stoichiometric relationship: [(Li 2 0). 26 (Fe 2 0 3 ). 2B ] x ⁇ Fe 2 0,) 1 ⁇ 0 ⁇ where .35 ⁇ x ⁇ .50 mole percent.
  • this composition range is represented by the cross-hatched portion of the ferrite/lithium ferrite phase diagram.
  • the desired formulation of such a lithium ferrite powder material which constitutes a carrier has a spinel structure, is environmentally safe, and has the necessary characteristics to serve as an excellent carrier.
  • the composition is prepared by the following sequential steps:
  • Lithium carbonate or lithium oxide is mixed with iron oxide in the amounts prescribed by the compositional formula set forth above.
  • the two compounds are intensely mixed by a wet or dry method.
  • the mixture of oxides is calcined to a temperature between 700° and 1 100°C as an optional step to prereact the mixture.
  • Calcined material or oxides from steps 1 and/or 2 are milled with water as a slurry in a milling unit such as an attritor or ball mill. To this slurry binders and deflocculants are added. Sintering aids may also be added to assist in densification and strength properties. Various other additives such as Si0 2 , Bi 2 0 3 , are typically added. This milling operation is ended when a desired particle size is achieved.
  • Slurry from the milling operation is spray dried to produce specified sized spheres referred to as beads. This operation is performed in a typical spray dryer using rotary or nozzle atomization.
  • Spray dried powder is screened to a specific size distribution in the green state. This operation is typically per ormed using a vibratory screening device.
  • Green screened product from the screening operation is sintered in a furnace or kiln in an atmosphere containing 21 % 0 2 capable of reaching temperatures of 1000°C to 1300°C. The degree of sintering depends upon the type of surface texture and apparent density desired. 7.
  • the fired powder typically exhibits some degree of bead to bead fusion and is, accordingly, deagglomerated with a hammer type of mill.
  • Deagglomerated powder is screened to a specific size distribution. Air classification may be used for separation or screening finer particle distributions.
  • Magnetic separation may be performed as an option to ensure that no non ⁇ magnetic particles are contained in the powder product.
  • the final sintered powder may be coated with a resin coating to assist in the attainment of the desired reprographic properties.
  • the present invention produces carriers with a variety of magnetic properties which may be used in different applications of magnetic brush development.
  • the following is a table which sets forth the range of magnetic saturation as it correlates with the composition.
  • lithium oxide ferrite carrier of the present invention Set forth below are some specific examples of the lithium oxide ferrite carrier of the present invention, and a comparison thereof to typical commercially produced
  • the carrier compositions are within the mole percentage range set forth in Figure 1 for the lithium oxide ferrite mixtures.
  • the example carriers are thus of the nature and have a crystalline structure which is principally a spinel structure.
  • the batches were intensively dry mixed in an Eirich R-7 mixer/pelletizer. After pelletization, two (2) gallons of water was added to minimize dusting and promote pelletization of the raw oxides and carbonates. The pellets were oven dried and calcined in a batch electric kiln for four (4) hours at 1010°C. Calcined pellets were charged to a batch type steel ball grinding mill and milled six (6) hours, with the following additives:
  • PVA polyvinyl styrene
  • Airvol 205S brand of PVA was used.
  • the slurry produced was nozzle atomized in a single fluid pressure nozzle type of dryer, using an 0.046 inch diameter orifice at 350psi to generate the appropriate bead size.
  • Spray dried powder or beads resulting therefrom was classified using a 48" diameter Sweco brand vibratory separator with the acceptable mesh fraction being - 120 TBC Mesh, + 200 TBC Mesh (-149// + 88//).
  • the resulting product was sintered at about 1 165°C for seven (7) hours in an air atmosphere in an electric fired batch kiln. Refractory boats were used to contain the powder during sintering.
  • the resultant powder cake was deagglomerated in a hammer type mill, and product again screened in a 48" Sweco vibratory separator -145 TBC Mesh, + 250 Market Grade Mesh (-125 + 63//).
  • the resultant carrier powder was then tested to determine its properties. Typical reprographic test properties are listed in Table 3.
  • Figures 2 and 3 depict the physical appearance of the carrier at 50 and 200 magnification utilizing a scanning electron microscope (SEM). The separate core elements are noted to be generally uniform in size and spherical.
  • Example No. 3 Copper zinc ferrite of the formulation (CuO) 0 . 20 (ZnO) 0 .n (Fe 2 0 3 ) o ⁇ was produced using processing like that of Example No. 1 with the exception that the calcine temperature was 790°C and final sintering temperature was 1300°C. Measured test properties are listed in Table 3. Figures 6 and 7 are SEM photomicrographs of the described prior art carrier and is offered for purposes of comparison to the carrier of Example No. 1 and No. 2. The size, shape and appearance is very similar to to the lithium ferrite carriers.
  • Example No. 4 Copper zinc ferrite of the formulation (CuO) 020 (ZnO) 0 . 26 (Fe 2 0 3 ) 0 BB was prepared using similar processing as in Example No. 1 with the exception that the calcining temperature was 790°C and the final sintering temperature was 1 160°C. Measured test properties are also listed in Table 3. Figures 8 and 9 are SEM photomicrographs of another prior art formulation for a carrier and for purposes of comparison should be evaluated in relation to Figures 2, 3, 4 and 5. Again the comparison is one of high similarity.
  • Example No. 5 Nickel zinc ferrite of the formulation (NiO). 1B ⁇ 3 (ZnO). 3220
  • a ferrite carrier core material composition preferably has several attributes to permit its use as a reprographic or electrographic carrier core material. For example, it should have the ability to adjust magnetic moment, Ms, similar to the carriers of Examples No. 3 and No. 4. This permits utilization in various copy machine designs.
  • the described nonstoichiometric lithium ferrite carrier permits similar variations as set forth in Table 1 and for Examples No. 1 and No. 2.
  • Bulk densities should be similar to the existing ferrite core materials.
  • the lithium ferrite carriers of the invention have a bulk density very similar to that of existing ferrite core materials. Also, by changing sintering temperatures and soak time at temperature, bulk density may be varied higher or lower depending on the desired value.
  • Flow rate determines the flow characteristics of a material in a copy machine magnetic brush developer station.
  • the lithium ferrite composition of the invention has very similar flow characteristics to that of pre-existing ferrite carriers. It is common for most carrier core materials to have either an acrylic, silicone, or fluoropolymer coating deposited on the carrier core surface to modify or enhance triboelectric or resistive properties for use with specific toners. For a new ferrite composition to comprise an acceptable substitute for existing coating technologies, it is important for surface texture, as measured by BEET surface area and visual observation by scanning electron microscopy, to show similar properties. Scanning electron microscopy analysis of Examples No. 1 through No.
  • the lithium ferrite carrier core of the invention is virtually indistinguishable from CuZn ferrite carrier core material and is similar to NiZn carrier core material. Comparison of BET surface area also shows very similar values. Also, BEET surface texture may be modified by adjustment of soak time, temperature, and processing conditions used to formulate the carrier core. Section 66699 of the State of California Administrative Code, Title 22, Division 4 lists offending elements that are (per soluble threshold limit concentration (STLC) and total threshold limit concentration (TTLC) limits) classified as a hazardous waste.
  • STLC per soluble threshold limit concentration
  • TTLC total threshold limit concentration
  • lithium ferrite materials which have a range of non-stoichiometric compositions and a spinel structure are deemed to be materials which are environmentally safe. That is, such materials can be utilized safely to provide a magnetic brush for the carrying of toner particles, and when the material is expended or no longer useful, it can be easily disposed without constituting an environmental hazard.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Compounds Of Iron (AREA)
  • Soft Magnetic Materials (AREA)

Abstract

Poudre non st÷chiométrique composée de ferrite et de lithium dont la plage de composition est representée par la formule [(Li2O)0,25 (Fe2O3)0,25]x (Fe2O3)1,00-x, dans laquelle 0,35 « x « 0,50 mole pour cent, qui constitue un véhicule sans danger pour l'environnement.
PCT/US1994/003843 1993-04-09 1994-04-07 Vehicule compose de ferrite et de lithium WO1994024613A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP94913384A EP0693191B1 (fr) 1993-04-09 1994-04-07 Vehicule compose de ferrite et de lithium
KR1019950704403A KR960702123A (ko) 1993-04-09 1994-04-07 리튬 페라이트 캐리어(lithium ferrite carrier)
DE69419742T DE69419742T2 (de) 1993-04-09 1994-04-07 Lithium-ferrit-träger
JP52331594A JP3429312B2 (ja) 1993-04-09 1994-04-07 リチウムフェライトキャリヤ

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4537993A 1993-04-09 1993-04-09
US08/045,379 1993-04-09

Publications (2)

Publication Number Publication Date
WO1994024613A1 true WO1994024613A1 (fr) 1994-10-27
WO1994024613B1 WO1994024613B1 (fr) 1994-12-08

Family

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PCT/US1994/003843 WO1994024613A1 (fr) 1993-04-09 1994-04-07 Vehicule compose de ferrite et de lithium

Country Status (7)

Country Link
EP (1) EP0693191B1 (fr)
JP (1) JP3429312B2 (fr)
KR (1) KR960702123A (fr)
CA (1) CA2160138A1 (fr)
DE (1) DE69419742T2 (fr)
TW (1) TW349187B (fr)
WO (1) WO1994024613A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997018498A1 (fr) * 1995-11-13 1997-05-22 Powdertech Corporation Support en ferrite de lithium

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59127054A (ja) * 1983-01-11 1984-07-21 Hitachi Metals Ltd 電子写真用現像剤
US4598034A (en) * 1982-09-13 1986-07-01 Nippon Iron Powder Co., Ltd. Ferrite carriers for electrophotographic development
JPS61200551A (ja) * 1985-03-01 1986-09-05 Mitsui Mining & Smelting Co Ltd 電子写真現像用キヤリヤ
WO1992005475A1 (fr) * 1990-09-14 1992-04-02 Eastman Kodak Company Composite en ferrite a trois phases interdispersees et particules porteuses electrographiques magnetiques obtenues a partir dudit composite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4598034A (en) * 1982-09-13 1986-07-01 Nippon Iron Powder Co., Ltd. Ferrite carriers for electrophotographic development
JPS59127054A (ja) * 1983-01-11 1984-07-21 Hitachi Metals Ltd 電子写真用現像剤
JPS61200551A (ja) * 1985-03-01 1986-09-05 Mitsui Mining & Smelting Co Ltd 電子写真現像用キヤリヤ
WO1992005475A1 (fr) * 1990-09-14 1992-04-02 Eastman Kodak Company Composite en ferrite a trois phases interdispersees et particules porteuses electrographiques magnetiques obtenues a partir dudit composite

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 29 (P - 540)<2476> 28 January 1987 (1987-01-28) *
PATENT ABSTRACTS OF JAPAN vol. 8, no. 257 (P - 316)<1694> 24 November 1984 (1984-11-24) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997018498A1 (fr) * 1995-11-13 1997-05-22 Powdertech Corporation Support en ferrite de lithium

Also Published As

Publication number Publication date
EP0693191A1 (fr) 1996-01-24
JPH08511108A (ja) 1996-11-19
DE69419742T2 (de) 1999-12-02
CA2160138A1 (fr) 1994-10-27
TW349187B (en) 1999-01-01
EP0693191B1 (fr) 1999-07-28
DE69419742D1 (de) 1999-09-02
JP3429312B2 (ja) 2003-07-22
KR960702123A (ko) 1996-03-28

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