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GB2118164A - SiO2-CaO-based low volumetrically-expansive flame- spraying material - Google Patents

SiO2-CaO-based low volumetrically-expansive flame- spraying material Download PDF

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Publication number
GB2118164A
GB2118164A GB08309102A GB8309102A GB2118164A GB 2118164 A GB2118164 A GB 2118164A GB 08309102 A GB08309102 A GB 08309102A GB 8309102 A GB8309102 A GB 8309102A GB 2118164 A GB2118164 A GB 2118164A
Authority
GB
United Kingdom
Prior art keywords
flame
sio2
cao
weight
spraying material
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.)
Granted
Application number
GB08309102A
Other versions
GB2118164B (en
Inventor
Hiroyuki Sugimoto
Kazuo Fukaya
Yoji Koguchi
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.)
Shinagawa Refractories Co Ltd
Japan Oxygen Co Ltd
JFE Engineering Corp
Taiyo Nippon Sanso Corp
Original Assignee
Shinagawa Refractories Co Ltd
Japan Oxygen Co Ltd
Nippon Sanso Corp
Nippon Kokan Ltd
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 Shinagawa Refractories Co Ltd, Japan Oxygen Co Ltd, Nippon Sanso Corp, Nippon Kokan Ltd filed Critical Shinagawa Refractories Co Ltd
Publication of GB2118164A publication Critical patent/GB2118164A/en
Application granted granted Critical
Publication of GB2118164B publication Critical patent/GB2118164B/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653Processes involving a melting step
    • C04B35/657Processes involving a melting step for manufacturing refractories
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66Monolithic refractories or refractory mortars, including those whether or not containing clay
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B29/00Other details of coke ovens
    • C10B29/06Preventing or repairing leakages of the brickwork
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00Casings; Linings; Walls; Roofs
    • F27D1/16Making or repairing linings ; Increasing the durability of linings; Breaking away linings
    • F27D1/1636Repairing linings by projecting or spraying refractory materials on the lining
    • F27D1/1642Repairing linings by projecting or spraying refractory materials on the lining using a gunning apparatus
    • F27D1/1647Repairing linings by projecting or spraying refractory materials on the lining using a gunning apparatus the projected materials being partly melted, e.g. by exothermic reactions of metals (Al, Si) with oxygen
    • F27D1/1652Flame guniting; Use of a fuel
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034Physico-chemical characteristics of the mixtures
    • C04B2111/00146Sprayable or pumpable mixtures
    • C04B2111/00155Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72Repairing or restoring existing buildings or building materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208Calcium oxide or oxide-forming salts thereof, e.g. lime
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427Silicates other than clay, e.g. water glass
    • C04B2235/3436Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3454Calcium silicates, e.g. wollastonite
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00Casings; Linings; Walls; Roofs
    • F27D1/16Making or repairing linings ; Increasing the durability of linings; Breaking away linings
    • F27D1/1636Repairing linings by projecting or spraying refractory materials on the lining
    • F27D1/1642Repairing linings by projecting or spraying refractory materials on the lining using a gunning apparatus
    • F27D1/1647Repairing linings by projecting or spraying refractory materials on the lining using a gunning apparatus the projected materials being partly melted, e.g. by exothermic reactions of metals (Al, Si) with oxygen
    • F27D1/1652Flame guniting; Use of a fuel
    • F27D2001/1663Fluid fuel, e.g. gas

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Ceramic Products (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

A flame-spraying material composed of a powder mixture having a particle size of not more than 0.5 mm and comprising 85 to 98% by weight of SiO2 and 2 to 15% by weight of CaO, and optionally 0.05 to 1.0% by weight of Li2O.

Description

SPECIFICATION SiO2-CaO-based low-volumetrically-expansive flame-spraying material The present invention relates to a flame-spraying material and in particular a flame-spraying material for repairing, by flame-spraying, any damaged part of a furnace or kiln such as a coke oven where a number of heating-and-cooling cycles are carried out.
Recently, repair of coke ovens by flame-spraying has been effected and outstanding effects have been demonstrated in relation to the repair time, the adhesive strength of the repaired part, durability, and the like. It has been known to employ a flame-spraying material containing about 70 wt.% SiO2, the material having a refractoriness of 11 000C to 1 2800C.
Coke ovens are lined with silica bricks having a coefficient of thermal expansion that rapidly increases between 3000C and 5000C and then keeps level without significant increase at temperatures in excess of 5000C. For this reason, silica bricks have a very high resistance to thermal spalling where they are used at temperatures over 5000 C. However, if the silica bricks are repaired, once they are damaged, with a flame-spray material comprising approximately 70% by weight of SiO2, no adequate endurance can be achieved at present as a result of the peeling off of the flame-sprayed coating due to the differences in the hot expansion behaviour between the base silica bricks and the flame-sprayed coating, which cause significant thermal stress therebetween as the flame-sprayed coating thermally expands linearly, contrary to silica bricks, up to about 10000 C.
Accordingly, what is desired is a flame-spraying material excellent in anti-spalling properties due to a very low hot thermal expansion rate as well as having hot thermal expansion behaviour similar to that of silica bricks.
The present invention provides a flame-spraying material comprising 85 to 98% by weight of SiO2 and 2 to 15% by weight of CaO and, optionally, 0.05 to 1.0% by weight of Li2O.
In a preferred embodiment, the flame-spraying material comprises a powder mixture having a particle size of not more than 0.5 mm and consisting of 85 to 98% by weight of SiO2, 2 to 15% by weight of CaO, optionally 0.05 to 1.0% by weight of Li2O, and the balance not more than 5% by weight of incidental impurities. The flame-spraying material may be adhered to the walls of a furnace while changing to a semi-molten or molten state in a flame resulting from the combustion of an oxygen-fuel gas mixture.
The flame-spraying material according to a first embodiment of the invention can be produced by combining silica based material such as silica, silica sand, or a silicate mineral and CaO-SiO2 based material such as Portland cement, wollastonite, ordicalcium silicate. As the CaO-SiO2 type raw material, preference should be given to Portland cement, wollastonite, and dicalcium silicate as given above, while uncombined CaO cannot be flame-sprayed. CaCO3 and Ca(OH)2 are less preferred owing to their high thermal loss resulting from the evolution of gases derived from their decomposition.
The flame-spraying material in a second embodiment according to the invention can be produced by combining silica based material such as silica, silica sand, or a silicate mineral, CaO-SiO2 based material such as Portland cement, wollastonite, or dicalcium silicate, and a lithium mineral such as spodumene or petalite. As to the silica based material and the CaO-SiO2 based material, preference should be given to those set forth in the first embodiment.
The flame-spraying material according to the invention shows a thermal expansion behaviour similar to that of silica bricks provided that the material has the compositions defined above. If the CaO content were less than 2% by weight, the viscosity of the fused material during flame-spraying using an oxygen-fuel combustion gas mixture couid not be reduced to an extent such that adequate fuseadhering could be achieved, because of the very high melt-viscosity of the remaining SiO2, thus resulting in an unsintered flame-sprayed coating, having a very low strength adhered coating, with a lower adhesion proportion.On the other hand, if CaO exceeded 15% by weight the flame-spraying material would more and more show a linearly increasing thermal expansion rate as a result of the gradual disappearance of the thermal expansion properties similar to those of silica bricks, thus showing an adverse propensity to peeling and damage. If the SiO2 content were less than 85% by weight or in excess of 98% by weight, this would give rise to adverse effects similar to those corresponding to the case if the CaO content exceeded 15% by weight or less than 2% by weight. Addition of Li20 permits one to achieve a low thermal expansion flame-spray coating.If the addition, however, were less than 0.05% by weight it would hardly have any effect on the thermal expansion properties; on the other hand, if it exceeded 1.0% by weight the refractoriness of the flame-sprayed coating would be decreased. If incidental impurities exist in excess of 5% by weight, the thermal expansion rate may tend to increase linearly, which is not preferable as set forth above. Particles larger than 0.5 mm in size do not melt completely in the flame of an oxygen-fuel combustion gas and most of them tend to be lost as a rebound loss, responsible for a lower adhering rate.
Flame-spraying materials according to the present invention have prominent technical significance over the prior art ones in that they show an improved adhesion rate of the flame-sprayed material and improved hot mechanical strength of the flame-sprayed coating due to the reduction of the meltviscosity of SiO2 stemming from the addition of CaO (and Li2O) in the specified amount, SiO2 along giving too high a melt-visocity and also a lower adhering rate along with a low mechanical strength deposited coating, and in that they make possible the suppression of peeling and damage to the deposited flame-sprayed coating by retaining a hot expansion behaviour similar to that of silica bricks.
The flame-spraying material can be used to repair a furnace in operation.
The following Examples are provided to illustrate, but not to limit, the present invention.
EXAMPLES -IV and COMPARATIVE EXAMPLES l'-ll' The flame-spray compositions indicated in the following Table 1 were prepared and were flamesprayed on silica brick using conventional techniques. The results are also shown in Table 1.
TABLE 1
Prior Art Example Present Invention Comparative Examples Examples Items I II Ill IV I' II' s Formulation chamotte 85 70 silica 90 80 80 90 silicate rock 5 white cement 10 wollastonite 10 20 10 5 sodium silicate anhydrous 15 30 Chemical Composition SiO2 93.4 88.7 85.8 93.7 65 66 CaO 4.8 9.7 11.4 2.4 impurities 1.8 1.6 2.8 3.9 - 35 34 Test Result adhesive strength (kg/cm2)* 100 80 75 90 10 6 bending strength (kg/cm2)* 170 150 120 110 15 12 adhesion rate ( /0) 70 85 80 70 75 80 No. of cycles until peeling No 45 40 No 20 15 occurs under a thermal peeling peeling cycle test** * values measured at 10000C ** substrate: silica brick; a cycle consists of changing the temperature between 1200"C and 300"C for 15 minutes, such cycles are repeated 50 times.
EXAMPLES V-lX and COMPARATIVE EXAMPES III'-IV' The flame-spray compositions indicated in the following Table 2 were prepared and were flamesprayed on silica brick using conventional techniques. The results are also shown in Table 2.
TABLE 2
Prior Art Example Present Invention Comparative Examples .Examples Items V < Vl l Vll | Vlil | IX - IV' Fommulation t Examples 80 75 .Examples chamotte = = = = = 85 75 silica 90 85 80 80 75 1 silica rock 10 white cement 3.5 8 wollastonite 5 5 15 12 spodumene - 5 petal it 1.5 15 5 5 sodium silicate anhydrous == == = 15 30 Chemical Composition I SiO2 94.0 94.0 92.5 90.2 85.6 65 66 CaO 2.1 2.3 2.2 6.5 10.4 Li2O 0.4 0.06 0.6 1 0.2 0.2 impurities 3.5 3.6 4.7 3.1 3.8 35 34 Test Results adhesive strength (kg/cm2)* 95 85 120 110 140 10. 6 bending strength (kg/cm2)* 115 100 - 135 170 180 15 12 adhesive rate (%) 80 75 90 80 85 75 80 No. of cycles until peeling No No No No No 20 15 occurs under a thermal peeling peeling peeling peeling peeling cycle test** Footnotes to Table 2.
* values measured at 1000"C ** substrate: silica brick; a cycle consists of changing the temperature between 1200"C and 300"C for 15 minutes, such cycles are repeated 50 times.
As seen from above Tables 1 and 2 the flame-spraying materials according to the invention show both better adhesion strength and bending strength than those of the prior art (comparative Example) and also show no peeling from the silica brick substrate in a heating-cooling thermal cycle test, thus showing superior properties over the prior art flame-spraying materials.

Claims (4)

1. A flame-spraying material comprising 85 to 98% by weight of SiO2 and 2 to 1 5% by weight of CaO.
2. A flame-spraying material comprising 85 to 98% by weight of SiO2, 2 to 1 5% by weight of CaO, and 0.05 to 1.0% by weight of Li2O.
3. A flame-spraying material as claimed in claim 1 or 2, in the form of a powder having a particle size of at most 0.5 mm.
4. Aflame-spraying material substantially as described in any of Examples I to IX.
GB08309102A 1982-04-02 1983-04-05 Sio2-cao-based low-volumetrically-expansive flame-spraying material Expired GB2118164B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57053755A JPS58172263A (en) 1982-04-02 1982-04-02 Sio2-cao low expansion flame spray material

Publications (2)

Publication Number Publication Date
GB2118164A true GB2118164A (en) 1983-10-26
GB2118164B GB2118164B (en) 1985-07-31

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Family Applications (1)

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GB08309102A Expired GB2118164B (en) 1982-04-02 1983-04-05 Sio2-cao-based low-volumetrically-expansive flame-spraying material

Country Status (4)

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JP (1) JPS58172263A (en)
DE (1) DE3311699C2 (en)
FR (1) FR2524462B1 (en)
GB (1) GB2118164B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2610318A1 (en) * 1987-02-03 1988-08-05 Nippon Steel Corp FLAME SPRAY MATERIAL WITH HIGH SILICON CONTENT
ES2041222A1 (en) * 1991-07-03 1993-11-01 Glaverbel Forming coherent refractory masses
US5686028A (en) * 1991-07-03 1997-11-11 Glaverbel Process for forming a coherent refractory mass on a surface

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60215579A (en) * 1984-04-06 1985-10-28 品川白煉瓦株式会社 Basic refractory composition for flame spraying
JPH0747197B2 (en) * 1992-01-27 1995-05-24 東京窯業株式会社 Nozzle for continuous casting of molten steel
JPH0747198B2 (en) * 1992-02-24 1995-05-24 明智セラミックス株式会社 Nozzle for continuous casting of molten steel
KR100369265B1 (en) * 1998-03-27 2003-01-24 가와사끼 세이데쓰 가부시키가이샤 Flame-spraying powdery repair mixture
JP4464804B2 (en) * 2004-11-30 2010-05-19 黒崎播磨株式会社 Thermal spraying material for industrial kiln repair
JP6263208B2 (en) * 2016-02-17 2018-01-17 品川リフラクトリーズ株式会社 Thermal spray material

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD48337A (en) *
GB621092A (en) * 1947-01-27 1949-04-04 Joseph Poulson Improvements relating to the treatment of gas retorts
DE839469C (en) * 1950-11-30 1952-05-19 Canadian Refractories Ltd Thermoplastic refractory materials
US3333840A (en) * 1964-11-30 1967-08-01 Harbison Walker Refractories Method of lining a metallurgical furnace and the product thereof
GB1225355A (en) * 1967-06-03 1971-03-17
FR2429762A1 (en) * 1978-06-29 1980-01-25 Carbonisation Entr Ceram Prodn. of refractory masonry for coke ovens - by vibratory moulding of refractory concrete
DE2913035A1 (en) * 1979-03-31 1980-10-02 Julius Aberle Building material using silicate aggregate, esp. silica sand - which is coated with enamel and then dielectrically heated to bond sand grains together via enamel

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2610318A1 (en) * 1987-02-03 1988-08-05 Nippon Steel Corp FLAME SPRAY MATERIAL WITH HIGH SILICON CONTENT
ES2041222A1 (en) * 1991-07-03 1993-11-01 Glaverbel Forming coherent refractory masses
US5686028A (en) * 1991-07-03 1997-11-11 Glaverbel Process for forming a coherent refractory mass on a surface

Also Published As

Publication number Publication date
FR2524462A1 (en) 1983-10-07
GB2118164B (en) 1985-07-31
DE3311699C2 (en) 1986-12-04
JPS6215508B2 (en) 1987-04-08
JPS58172263A (en) 1983-10-11
FR2524462B1 (en) 1987-01-16
DE3311699A1 (en) 1983-10-13

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19940405