NO126730B - - Google Patents

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NO126730B
NO126730B NO04450/70A NO445070A NO126730B NO 126730 B NO126730 B NO 126730B NO 04450/70 A NO04450/70 A NO 04450/70A NO 445070 A NO445070 A NO 445070A NO 126730 B NO126730 B NO 126730B
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volume percent
titanium carbide
titanium nitride
powder
molybdenum
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NO04450/70A
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Norwegian (no)
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Horacio Enrique Bergna
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Du Pont
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    • 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
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5611Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
    • 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
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/58007Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
    • C04B35/58014Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on titanium nitrides, e.g. TiAlON
    • 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
    • C04B35/64Burning or sintering processes
    • C04B35/645Pressure sintering
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/16Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S75/00Specialized metallurgical processes, compositions for use therein, consolidated metal powder compositions, and loose metal particulate mixtures
    • Y10S75/95Consolidated metal powder compositions of >95% theoretical density, e.g. wrought

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)
  • Powder Metallurgy (AREA)
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Description

Oppfinnelsen angår titannitrid-titancarbidmaterialer bundet The invention relates to bonded titanium nitride-titanium carbide materials

med nikkel-molybden. with nickel-molybdenum.

Det er en omfattende litteratur angående skjæreverktøy av metallbundet nitrid-carbid, som f.eks. U.S. patenter 1895959 og nr. 1996220, og mer nylig nr. 3<1>+09<l>+l6 og nr. 3^09^19. Ingen av disse publikasjoner angir imidlertid et materiale av titannitrid-titancarbid bundet med en nikkel-molybdenblanding. There is extensive literature regarding metal-bonded nitride carbide cutting tools, such as U.S. patents 1895959 and No. 1996220, and more recently No. 3<1>+09<l>+16 and No. 3^09^19. None of these publications, however, state a material of titanium nitride-titanium carbide bonded with a nickel-molybdenum mixture.

Det har ifolge oppfinnelsen vist seg at titannitrid og titancarbid bundet med blandinger av nikkel og molybden ved varmpressing danner tette, finkornede gjenstander som har en meget hoy fasthet og er harde og motstandsdyktige overfor slitasje, skraping, oxydasjon og korrosjon. According to the invention, it has been shown that titanium nitride and titanium carbide bonded with mixtures of nickel and molybdenum by hot pressing form dense, fine-grained objects that have a very high strength and are hard and resistant to wear, scratching, oxidation and corrosion.

Oppfinnelsen'angår et ildfast materiale som angitt i patent-krav 1's overbegrep og som er særpreget ved at det består av H9,5- The invention' relates to a refractory material as stated in the preamble of patent claim 1 and which is characterized by the fact that it consists of H9.5-

9<*>+ volumprosent titannitrid, 5-Lt-9,5 volumprosent titancarbid og 1- 9<*>+ volume percent titanium nitride, 5-Lt-9.5 volume percent titanium carbide and 1-

15 volumprosent metall bestående i det vesentlige av 20-50 volumprosent nikkel og 50-8o volumprosent molybden, idet materialet har en tetthet over 99% av den. teoretiske og en gjennomsnittlig kornstorrelse under 2/im. 15 volume percent metal consisting essentially of 20-50 volume percent nickel and 50-80 volume percent molybdenum, the material having a density above 99% of it. theoretical and an average grain size below 2/im.

Oppfinnelsen angår.også en fremgangsmåte ved fremstilling av slike ildfaste materialer, og fremganjgsmåten er særpreget ved at en homogen blanding av k$.5-9^ volumprosent titannitrid, 5-^9,5 volumprosent titancarbid og 1-15 volumprosent metall bestående i det vesentlige av 20-50 volumprosent nikkel og 50-80 volumprosent molybden oppvarmes til en temperatur av 1600-1900°C, og at blandingen ved denne temperatur presses ved et trykk av 70,3-351,5 kg/cm o, hvorpå det dannede presstykke hurtig avkjoles. The invention also relates to a method for the production of such refractory materials, and the method is characterized by a homogeneous mixture of 5-9% by volume titanium nitride, 5-9.5% by volume titanium carbide and 1-15% by volume metal consisting of substantially of 20-50 volume percent nickel and 50-80 volume percent molybdenum is heated to a temperature of 1600-1900°C, and that the mixture at this temperature is pressed at a pressure of 70.3-351.5 kg/cm o, whereupon the formed press piece is quickly cooled.

De fremstilte tette materialer er nyttige for fremstilling av gjenstander som er motstandsdyktige overfor slitasje og korrosjon og som har en usedvanlig hoy fasthet og hardhet og som kan bearbeides til tiltalende smykkegjenstander. The produced dense materials are useful for the production of articles which are resistant to wear and corrosion and which have an exceptionally high strength and hardness and which can be processed into attractive pieces of jewellery.

Titannitrid og titancarbid som er egnet for anvendelse ved fremstilling av det ildfaste materiale ifolge oppfinnelsen, bor ha en gjennomsnittlig partikkelstorrelse av under 1^m, fortrinnsvis under o,5 m. Titanium nitride and titanium carbide which are suitable for use in the production of the refractory material according to the invention should have an average particle size of less than 1 µm, preferably less than 0.5 µm.

Et egnet titannitrid er tilgjengelig i handelen i form av et A suitable titanium nitride is commercially available in the form of a

-325 mesh pulver eller det kan fremstilles på vanlige måter som beskrevet i U.S. patenter nr. 3<l>f09<1>+l6 og nr. 3<1>f09<L>+19 eller i "Nitrides", kapittel VIII, i boken "High Temperature Technology" av J.M. Blocher Jr., John Wiley & Sons, N.Y. 1956. Et egnet titancarbid er tilgjengelig i handelen i form av et -325 mesh pulver eller det kan fremstilles på vanlige velkjente måter. -325 mesh powder or it may be prepared by conventional means as described in U.S. Pat. patents No. 3<l>f09<1>+l6 and No. 3<1>f09<L>+19 or in "Nitrides", Chapter VIII, in the book "High Temperature Technology" by J.M. Blocher Jr., John Wiley & Sons, N.Y. 1956. A suitable titanium carbide is commercially available in the form of a -325 mesh powder or it can be prepared by conventional well known methods.

Dersom titannitridet eller titancaibidet har en for stor partikkelstorrelse, kan det findeles ved ganske enkelt å male titannitridet inntil den onskede partikkelstorrelse er blitt oppnådd. If the titanium nitride or titanium carbide has an excessively large particle size, it can be refined by simply grinding the titanium nitride until the desired particle size has been achieved.

Metallpulvere som er egnede for anvendelse ifolge oppfinnelsen, bor ha en partikkelstorrelse under 10^m, fortrinnsvis under 2/Lim. Metal powders which are suitable for use according to the invention should have a particle size below 10 µm, preferably below 2/Lim.

. Et egnet nikkelpulver er tilgjengelig i handelen eller det . A suitable nickel powder is commercially available or it

kan fremstilles på vanlige velkjente måter. can be produced in conventional well-known ways.

Et egnet molybdenpulver er tilgjengelig i handelen i form A suitable molybdenum powder is commercially available in form

av et -325 mesh pulver eller det kan fremstilles på vanlige velkjente måter. , of a -325 mesh powder or it can be prepared by conventional well-known methods. ,

De fire bestanddeler bor fortrinnsvis være helt rene, og det er spesielt viktig åt de er i det vesentlige frie for forurensninger, som oxygen, som har skadelige virkninger på de faste opp-løsninger som dannes ved foreliggende fremgangsmåte. Mindre mengder av forurensninger som vanligvis taes opp ved malingen eller blandingen av bestanddelene, har liten eller ingen skadelig virkning på de ildfaste materialer. Små mengder lavtsmeltende metaller, som kobolt eller jern, eller hoyeresmeltende metaller, som wolfram, The four components should preferably be completely pure, and it is particularly important that they are essentially free of contaminants, such as oxygen, which have harmful effects on the solid solutions formed by the present method. Smaller amounts of contaminants, which are usually taken up during the painting or mixing of the components, have little or no harmful effect on the refractory materials. Small amounts of low-melting metals, such as cobalt or iron, or high-melting metals, such as tungsten,

som vanligvis forekommer i måleutstyr eller -media, kan således tolereres på samme måte som små mengder av ildfaste materialer, which usually occurs in measuring equipment or media, can thus be tolerated in the same way as small amounts of refractory materials,

som carbider, nitrider eller oxyder, som forekommer under den ovenfor angitte håndtering. such as carbides, nitrides or oxides, which occur during the above-mentioned handling.

Som angitt ovenfor anvendes titannitridet i materialene ifolge oppfinnelsen i en mengde av<*>+9,5-9^ volumprosent. Det anvendes fortrinnsvis i en mengde av 60-85 volumprosent da slike mengder gir et ildfast materiale med en meget onskelig kombinasjon av egenskaper og utseende. Dersom titannitrid anvendes i en mengde av 60-85 volumprosent, foretrekkes det å anvende 12-30 volumprosent titancarbid og 3-10 volumprosent metall. As indicated above, the titanium nitride is used in the materials according to the invention in an amount of +9.5-9% by volume. It is preferably used in an amount of 60-85% by volume as such amounts give a refractory material with a very desirable combination of properties and appearance. If titanium nitride is used in an amount of 60-85 volume percent, it is preferred to use 12-30 volume percent titanium carbide and 3-10 volume percent metal.

Det antaes at molybden trenger inn i titancarbidgitteret, og det foretrekkes at et stort overskudd av metall utover den mengde som det antaes kan taes opp i titancarbidgitteret, ikke er tilstede. Dette er begrunnet med at et stort overskudd av metall ned-setter de ildfaste materialers motstandsdyktighet- overfor korr-sjon , og skraping og hardhet. Det foretrekkes derfor at det i de foreliggende materialer ikke er tilstede mer. enn 1 volumdel metall pr. volumdel titancarbid. It is assumed that molybdenum penetrates the titanium carbide lattice, and it is preferred that a large excess of metal beyond the amount which it is assumed can be taken up in the titanium carbide lattice is not present. This is justified by the fact that a large excess of metal reduces the refractory materials' resistance to corrosion, scratching and hardness. It is therefore preferred that no more is present in the present materials. than 1 volume part of metal per volume part titanium carbide.

Blandingene av pulverbestanddelene fremstilles på lignende måte som beskrevet i U.S. patent nr.. 3<1>+5l791. Det er gunstig homogent å blande titannitrid, titancarbid, nikkel og.molybden av den ovenfor angitte type, f.eks. ved kulemolling, i inntil 120 timer eller derover. De blandede pulvere blir derefter varmpresset ved en temperatur av 1650-1900°C, fortrinnsvis 1750-l850°C, og et trykk av 70,3-351,5 kg/cm 2, fulgt av en hurtig avkjoling av press-stykket på den i U.S. patent nr. 3^51791 beskrevne måte. The mixtures of the powder ingredients are prepared in a similar manner as described in U.S. Pat. patent no.. 3<1>+5l791. It is beneficial to homogenously mix titanium nitride, titanium carbide, nickel and molybdenum of the above type, e.g. by ball moulding, for up to 120 hours or more. The mixed powders are then hot-pressed at a temperature of 1650-1900°C, preferably 1750-1850°C, and a pressure of 70.3-351.5 kg/cm 2 , followed by a rapid cooling of the press piece on the in the U.S. patent no. 3^51791 described manner.

De varmpressede,. ildfaste presstykker er særpreget ved at de har en porositet under 1$, som gir seg tilkjenne ved en tetthet, av minst 99% av den teoretiske, og en gjennomsnittlig kornstorrelse av under 2/im. Som angitt ovenfor inneholder d.e foretrukne materialer ifolge oppfinnelsen 60-85 volumprosent titannitrid, 12-30 volumprosent titancarbid og 3-10 volumprosent metall og har en gjennomsnittlig kornstorrelse av under 1 ym. De foreliggende materialers kjemiske innhold og fysikalske egenskaper kan bestemmes ved anvendelse av velkjente metoder som detaljert beskrevet i U.S. patenter nr. 3^09^16, nr. 3<1>+09<1>+19, nr. 3^13392 og nr. 3^51791 som det er vist til ovenfor. The hot pressed,. Refractory pressed pieces are characterized by having a porosity of less than 1$, which is indicated by a density of at least 99% of the theoretical, and an average grain size of less than 2/im. As indicated above, the preferred materials according to the invention contain 60-85 volume percent titanium nitride, 12-30 volume percent titanium carbide and 3-10 volume percent metal and have an average grain size of less than 1 um. The chemical content and physical properties of the present materials can be determined using well-known methods as detailed in U.S. Pat. patents No. 3^09^16, No. 3<1>+09<1>+19, No. 3^13392 and No. 3^51791 as referred to above.

De ildfaste materialer- ifolge oppfinnelsen foreligger som faste opplbsninger med en Rockwell A hardhet av 92- ca. 9^ og en boyningshastighet fra ca. l*+06l til nesten 22850 kg/cm . Denne kombinasjon av fasthet og hardhet sammen med materialenes lave porositet, fine kornstorrelse og ildfasthet gjor materi?lene ifolge oppfinnelsen nyttige for anvendelser hvor det er nodvendig med motstandsdyktighet overfor korrosjon, oxydasjon, skraping og slitasje. De er spesielt nyttige for skjæring og dreining av metaller. Des tuten gjor deres tydelige farve kombinert med deres motstandsdyktighet overfor skraping og riss dem onskelige for anvendelse i smykkegjenstander, som urkasser. The refractory materials according to the invention are available as solid solutions with a Rockwell A hardness of 92 - approx. 9^ and a buoyancy speed from approx. l*+06l to almost 22850 kg/cm . This combination of firmness and hardness together with the materials' low porosity, fine grain size and refractoriness make the materials according to the invention useful for applications where resistance to corrosion, oxidation, scratching and wear is required. They are particularly useful for cutting and turning metals. Their distinct color combined with their resistance to scratches and scratches makes them undesirable for use in jewelry, such as watch cases.

I eksemplene er alle deler og prosenter basert på vekt der san intet annet er angitt. In the examples, all parts and percentages are based on weight unless otherwise stated.

Eksempel 1 Example 1

Dette er et eksempel på et materiale innenoldende 65 volumprosent titannitrid, 30 volumprosent titancarbid, 2,5 volumprosent metallisk molybden og 2,5 volumprosent metallisk nikkel. This is an example of a material containing 65 volume percent titanium nitride, 30 volume percent titanium carbide, 2.5 volume percent metallic molybdenum and 2.5 volume percent metallic nickel.

Det anvendte titannitrid var av kvalitet -325 mesh og hadde The titanium nitride used was of -325 mesh quality and had

et spesifikt overflateareal av 1,1 m 2/g bestemt ved ni.trogenadsorp-sjon.. ht elektronmikrofotografi av titannitridet viste at det besto av tette, uregelmessige partikler med en storrelse av 1- ca. lOMm, idet hoveddelen av partiklene hadde en størrelse av 1 - 2 um. Carboninnholdet var 0,33% og oxygeninnholdet 0,87%. En kjemisk analyse viste at det inneholdt 76^19 % titan og 18,71 % nitrogen. a specific surface area of 1.1 m 2 /g determined by nitrogen adsorption. ht electron micrograph of the titanium nitride showed that it consisted of dense, irregular particles with a size of 1- approx. lOMm, the main part of the particles having a size of 1 - 2 µm. The carbon content was 0.33% and the oxygen content 0.87%. A chemical analysis showed that it contained 76^19% titanium and 18.71% nitrogen.

Det anvendte titancarbidpulver hadde en gjennomsnittlig partikkelstorrelse av 0,6pm målt med en Fisher Sub-Sieve Sizer og et spesifikt overflateareal av ca. 10 m 2/g bestemt ved nitrogenadsorpsjon. Et elektronmikrofotografi av en torrmontert prove viste at titancarbidkornene hadde en diameter av 0,2-3^irn og at de av og til var samlet i form av lese aggregater. Titaninnholdet var ca. 77,8%, det samlede carboninnhold ca. 18,8 %, innholdet av fritt carbon ca. 0,07% og oxygeninnholdet ca. 0,8-1,6%. En analyse ved emisjons-spektroskopi viste at titan var hovedbestanddelen og dessuten at del inneholdt 0,5-2 % molybden, 0,5 - 2 % wolfram, 0,5 - 2 % nikkel, 500-2500 ppm (deler pr. million) aluminium, 200-1000 ppm kobolt, 300-1500 ppm jern, 300-1500 ppm niob, 200-1000 ppm krom, 200- The titanium carbide powder used had an average particle size of 0.6 pm measured with a Fisher Sub-Sieve Sizer and a specific surface area of approx. 10 m 2/g determined by nitrogen adsorption. An electron micrograph of a dry-mounted sample showed that the titanium carbide grains had a diameter of 0.2-3 µm and that they were occasionally collected in the form of loose aggregates. The titanium content was approx. 77.8%, the total carbon content approx. 18.8%, the content of free carbon approx. 0.07% and the oxygen content approx. 0.8-1.6%. An analysis by emission spectroscopy showed that titanium was the main component and also that part contained 0.5-2% molybdenum, 0.5-2% tungsten, 0.5-2% nickel, 500-2500 ppm (parts per million) aluminium, 200-1000 ppm cobalt, 300-1500 ppm iron, 300-1500 ppm niobium, 200-1000 ppm chromium, 200-

1000 ppm silicium, 100-500 ppm zirkonium, 50-250 ppm kalsium, 50-250 ppm mangan og 5-25 ppm magnesium. 1000 ppm silicon, 100-500 ppm zirconium, 50-250 ppm calcium, 50-250 ppm manganese and 5-25 ppm magnesium.

Det anvendte molybdenpulver var av i handelen tilgjengelig standard kvalitet med en kornstorrelse av under 325 mesh, et spesifikt overflateareal bestemt ved nitrogenadsorpsjon av 0,29 m /g og en gjennomsnittlig krystallstorrelse av 35<*>+ nm bestemt ved rontgendiffraksjon med linjeutvidelse. Et elektronmikrofotografi viste at molybdenpulveret besto av korn med en diameter av 0,5- The molybdenum powder used was of commercially available standard quality with a grain size of less than 325 mesh, a specific surface area determined by nitrogen adsorption of 0.29 m /g and an average crystal size of 35<*>+ nm determined by X-ray diffraction with line broadening. An electron micrograph showed that the molybdenum powder consisted of grains with a diameter of 0.5-

3^m pakket sammen i form av åpne aggregater. En kjemisk analyse av pulveret viste at det inneholdt 052 % ozygen og ingen forurensninger i en mengde over 500 ppm. 3^m packed together in the form of open aggregates. A chemical analysis of the powder showed that it contained 0.52% oxygen and no impurities in an amount above 500 ppm.

Det anvendte nikkel var et i handelen tilgjengelig findelt pulver inneholdende 0,15 % carbon, 0,07 % oxygen og under 300 ppm jern. Nikkelpulverets spesifikke overf lateareal var 0,^+8 rn 2/g , og dets rontgendiffråksjonsmonster viste bare nikkel som ved linjeutvidelse ble bestemt å ha en krystallstorrelse av 150 nm. Under et elektronmikroskop viste pulveret seg å bestå av kornaggregater med en diameter av 1-5 ym. The nickel used was a commercially available finely divided powder containing 0.15% carbon, 0.07% oxygen and less than 300 ppm iron. The specific surface area of the nickel powder was 0.^+8 rn 2 /g , and its X-ray diffraction sample showed only nickel determined by line broadening to have a crystal size of 150 nm. Under an electron microscope, the powder turned out to consist of grain aggregates with a diameter of 1-5 um.

Pulverne ble malt ved å fylle 6000 deler på forhånd kondi-sjonerte sylindriske koboltbundne wolframcarbidinnsatsstykker med en lengde av 6,35 mm og en diameter av 6,35 mm i en 1,3 liters stål-kulemolle med en diameter av ca. 15, 2h cm idet 290 deler "Soltrol" 130 mettet paraffinisk hydrocarbon med et kokepunktsområde av 165-210°C også ble ifylt. Mollen ble derefter fylt med 105,9 deler titannitrid, W+,5 deler titancarbid, 7,6 deler molybdenpulver og 6,6 deler nikkelpulver av de kvaliteter som er beskrevet ovenfor. The powders were milled by filling 6000 parts of pre-conditioned cylindrical cobalt-bonded tungsten carbide inserts 6.35 mm in length and 6.35 mm in diameter into a 1.3 liter steel ball mill with a diameter of approx. 15.2h cm in which 290 parts of "Soltrol" 130 saturated paraffinic hydrocarbon with a boiling point range of 165-210°C were also filled. The mold was then filled with 105.9 parts titanium nitride, W+.5 parts titanium carbide, 7.6 parts molybdenum powder and 6.6 parts nickel powder of the grades described above.

Mollen ble derefter lukket og omdreiet med 90 omdreininger The mold was then closed and rotated 90 revolutions

pr. minutt i 5 dager. Mollen ble derefter åpnet og innholdet tomt per minute for 5 days. The case was then opened and the contents emptied

ut mens maleinnsatsstykkene ble holdt tilbake. Mollen ble derefter skylt flere ganger med "Soltrol" 130 inntil alle malte faste stoffer var blitt fjernet. out while the paint inserts were retained. The mold was then rinsed several times with "Soltrol" 130 until all painted solids had been removed.

Det malte pulver ble derefter overfort til et vakuumfordamp-ningsapparat, og overskuddet av hydrocarbon ble dekantert av efter at det suspenderte materiale var blitt bunnavsatt. Den fuktige restkake ble derefter torket under vakuum med tilforsel av varme inntil temperaturen i fordampningsapparatet var 200-300°C og trykket under ca. 0,1 mmHg. Pulveret ble derefter håndtert under fullstendig utelukkelse av luft. The ground powder was then transferred to a vacuum evaporation apparatus, and the excess hydrocarbon was decanted off after the suspended material had settled to the bottom. The moist residual cake was then dried under vacuum with the supply of heat until the temperature in the evaporation apparatus was 200-300°C and the pressure below approx. 0.1mmHg. The powder was then handled under complete exclusion of air.

Det torre pulver ble fort gjennom en 70 mesh sikt under en nitrogenatmosfære og derefter lagret under nitrogen i lukkede plast-beholdere. The dry powder was passed through a 70 mesh sieve under a nitrogen atmosphere and then stored under nitrogen in closed plastic containers.

Et presset råemne ble fremstilt fra pulveret ved å varmpresse dette i en sylindrisk grafittform med et formhulrom med et kvadratisk tverrsnitt av 2,7 x 2,7 cm og forsynt med motsatt rettede, tett-sluttende stempler. Et stempel ble holdt på plass i en ende av formhulrommet mens 31 deler av pulveret ble fylt i formhulrommet under nitrogen og jevnt fordelt ved å omdreie formen og banke den lett på siden. Det ovre stempel ble derefter satt på plass for hånd. Den sammenstilte form og innholdet ble derefter anbragt i et vakuumkammer i en vakuumvarmpresse idet formen ble holdt i lodd-rett stilling, og det ovre og undre stempel ble på- A pressed blank was prepared from the powder by hot-pressing it in a cylindrical graphite mold with a mold cavity having a square cross-section of 2.7 x 2.7 cm and provided with oppositely directed, close-fitting pistons. A plunger was held in place at one end of the mold cavity while 31 parts of the powder was filled into the mold cavity under nitrogen and evenly distributed by rotating the mold and tapping it lightly on its side. The upper stamp was then put in place by hand. The assembled mold and its contents were then placed in a vacuum chamber in a vacuum hot press, the mold being held in a vertical position, and the upper and lower pistons were

virket av motsatt rettede grafittstotere i pressen med et trykk av ca. h2 kg/cm . Formen ble i lopet av 1 minutt hevet inn i ovnens varmesone med en temperatur av 1175°C, og ovnstemperaturen ble straks oket til l800°C i lopet av 10 minutter og formens temperatur holdt på l800°C i ytterligere 2 minutter for å sikre en jevn opp-varming av proven. Et trykk av 28l kg/cm 2 ble derefter påfort via stemplene i h minutter. Straks efter pressingen ble formen og innholdet mens det ble holdt mellom de motsatt rettede stbtere, overfort fra ovnen til en kjblesone hvor formen og innholdet ble av-kjolt til svak rbdglod i lopet av ca. 5 minutter. worked by oppositely directed graphite pushers in the press with a pressure of approx. h2 kg/cm . In the course of 1 minute, the mold was raised into the oven's heating zone with a temperature of 1175°C, and the oven temperature was immediately increased to 1800°C in the course of 10 minutes and the mold's temperature was kept at 1800°C for a further 2 minutes to ensure a uniform heating of the sample. A pressure of 28l kg/cm 2 was then applied via the pistons for h minutes. Immediately after the pressing, the mold and contents, while held between the oppositely directed staves, were transferred from the oven to a cooling zone where the mold and contents were cooled to a faint red glow over the course of approx. 5 minutes.

Formen og innholdet ble derefter fjernet fra vakuumovnen og råemnet fjernet fra formen og blåst med slipekorn for å fjerne eventuelt vedheftende carbon. The mold and contents were then removed from the vacuum oven and the blank removed from the mold and blasted with abrasive grit to remove any adhering carbon.

Det ferdige stykkes tetthet bestemt ved nbyaktig veiing og måling av dimensjonene var 5,^8 g/cm<J>og tilsvarte den teoretiske The density of the finished piece determined by close weighing and measurement of the dimensions was 5.8 g/cm<J> and corresponded to the theoretical

tetthet. density.

Det varmpressede materiale viste seg ved undersøkelse ved • 1000 X forstørrelse å være i det vesentlige uporost. Denne egen-skap er viktig da uporbse materialer er mor motstandsdyktige overfor korrosjon enn porose materialer med den samme kjemiske sammen-setning. Materialet besto strukturmessig av et meget fint nett-verk. Porøsiteten basert på optiske mikxofotografier var A 1/A2 ifolge ASTM's porositetsskala. The hot-pressed material proved to be essentially uncorroded when examined at • 1000 X magnification. This property is important as porous materials are more resistant to corrosion than porous materials with the same chemical composition. Structurally, the material consisted of a very fine net work. The porosity based on optical microphotographs was A 1/A2 according to the ASTM porosity scale.

Elektronmikrofotografier antydet en meget finkornet struktur med få korn med en størrelse over 1 eller 2 /Lim. Dessuten viste elektronmikrofotografier en intragranulær fase eller grunnmassefase. Det forekom fra mikrotfotografiet som om metallfasen fullstendig fuktet Litancarbid-titannitridfasen eller -fasene. Electron micrographs suggested a very fine-grained structure with few grains with a size above 1 or 2 /Lim. Moreover, electron micrographs showed an intragranular or groundmass phase. It appeared from the micrograph that the metal phase completely wetted the Litan carbide-titanium nitride phase or phases.

Proven var meget seig og gikk ikke i stykker.eller ble avskallet ved fritt fall mot et hårdvedgulv fra en hoyrfe av 2,13 m. The sample was very tough and did not break or flake off when free-falling onto a hardwood floor from a 2.13 m high horse.

Proven ble polert ved å presse dens overflater fast mot roter-ende skiver med diamantimpregnert duk. For dette ble en Beuhler poleringsmaskin anvendt. En ^-00 korns diamantskive ble anvendt ved 1175 omdreininger pr. minutt for det forste poleringstrinn -og en 1000 korns diamantskive ved 550 omdreininger pr. minutt for det annet, avsluttende trinn. The sample was polished by pressing its surfaces firmly against rotating discs with diamond-impregnated cloth. For this, a Beuhler polishing machine was used. A ^-00 grain diamond wheel was used at 1175 revolutions per minute. minute for the first polishing step - and a 1000 grain diamond disc at 550 revolutions per minute. minute for the second, final step.

Den på denne måte polerte prove hadde et tiltalende ornament-lignende utseeende med en gylden farve. The sample polished in this way had an attractive ornament-like appearance with a golden color.

En annen prove med den samme størrelse ble fremstilt som angitt ovenfor, og 1,778 x 1,778 mm kvadratiske prbvestenger for bbyningsfåsthet ble skåret ut på hver side av et midtstykke. Deler av proven ble anvendt for undersøkelse av hardheten mot inntrengning og andre produktegenskaper. Bøyningsfasthet målt ved bøyning' av de 1,778 x 1,778 mm prøvestaver over et 1^,29 mm spenn var ca.21092 kg/cm 2. Rockwell A hardheten var 93?0. Another specimen of the same size was prepared as indicated above, and 1.778 x 1.778 mm square bending resistance test bars were cut on each side of a center piece. Parts of the sample were used to examine the hardness against penetration and other product properties. Flexural strength measured by bending the 1.778 x 1.778 mm test bars over a 1/29 mm span was approximately 21092 kg/cm 2 . Rockwell A hardness was 93?0.

En av de for boyningsfasthetmålingen anvendte stenger ble knust og malt i en morter av carbonståi, og det derved oppnådde pulver ble anvendt for rontgenanalyse. Det oppnådde rbntgendiagram viste et utpreget flatesentrert kubisk monster med en gitterpara-meter av W,2678. Dette monster tilsvarer en fast oppløsning av titannitrid-titancarbid. Gitterparameterne for flatesentrert kubisk titannitrid og titancarbid er hhv. ca. h , 2. k og ca. '•f,32. One of the rods used for the bending strength measurement was crushed and ground in a mortar made of carbon steel, and the resulting powder was used for X-ray analysis. The obtained X-ray diagram showed a distinct face-centered cubic monster with a lattice parameter of W.2678. This monster corresponds to a solid solution of titanium nitride-titanium carbide. The lattice parameters for face-centered cubic titanium nitride and titanium carbide are respectively about. h , 2nd k and approx. '•f,32.

Alle gitterparametere er angitt i kX enheter. All lattice parameters are given in kX units.

Materialet ifolge eksemplet hadde en utmerket motstandsdyktighet overfor oxydasjon og korrosjon og var motstandsdyktig overfor varmesjokk og skraping og hadde lav reaktivitet overfor metaller. The material according to the example had excellent resistance to oxidation and corrosion and was resistant to thermal shock and scratching and had low reactivity towards metals.

Den usedvanlige kombinasjon av hoy fasthet og hoy hardhet sammen med de ovenfor angitte egenskaper gjor at materialet ifolge eksemplet er et utmerket materiale for slitasjedeler, korrosjons-resistente deler og skjærende verktoy for maskinering av metaller. The extraordinary combination of high strength and high hardness together with the above-mentioned properties makes the material, according to the example, an excellent material for wear parts, corrosion-resistant parts and cutting tools for machining metals.

Polerte prover av materialet kan også anvendes som smykkegjenstander. Polished samples of the material can also be used as jewelery items.

Eksempel 2 Example 2

Fremgangsmåten ifolge eksempel 1 ble gjentatt, men med den forandring at bestanddelene ble anvendt i slike mengder at det hie oppnådd et materiale inneholdende 88,5 volumprosent titannitrid, 10 volumprosent titancarbid, 1 volumprosent metallisk molybden og 0,5 volumprosent nikkel. The procedure according to example 1 was repeated, but with the change that the components were used in such quantities that a material containing 88.5 volume percent titanium nitride, 10 volume percent titanium carbide, 1 volume percent metallic molybdenum and 0.5 volume percent nickel was obtained.

De virkelige mengder som ble fylt i 1,3 liters stålmollen, The actual quantities that were filled in the 1.3 liter steel mold,

var lMt.,20 deler titannitridpulver, lM-,8l deler titancarbidpulver, 3,66 deler metallisk molybdenpulver og 0,89 deler metallisk nikkelpulver. was 1Mt.20 parts titanium nitride powder, 1M-.81 parts titanium carbide powder, 3.66 parts metallic molybdenum powder and 0.89 parts metallic nickel powder.

Et kvadratisk råemne fremstilt som angitt i eksempel 1 og med et tverrsnitt av 2,70 cm og en tykkelse av ca. 0,76 cm ble oppdelt slik at prøvestykker med en storrelse av 1,778 x 1,778 x 25,^ mm ble skåret ut fra begge sider av et midtstykke. A square blank produced as indicated in example 1 and with a cross section of 2.70 cm and a thickness of approx. 0.76 cm was divided so that test pieces measuring 1.778 x 1.778 x 25.5 mm were cut from both sides of a center piece.

Stengene ble anvendt for boyningsfasthetsmålinger, og den opp-nå© dde verdi var 1933'+ kg/cm 2. Resten av provene ble anvendt for hardhetsmåling og for andre undersøkelser. Den gjennomsnittlige Rockwell A hardhet var 93 >2. The bars were used for bending strength measurements, and the value reached was 1933'+ kg/cm 2. The rest of the sample was used for hardness measurements and for other investigations. The average Rockwell A hardness was 93 >2.

Tettheten var 5,^5 g/cm^ eller over 99% av den teoretiske. The density was 5.5 g/cm^ or over 99% of the theoretical.

Materialet ifolge eksemplet hadde en utmerket motstandsdyktighet overfor oxydasjon og korrosjon og var motstandsdyktig overfor varmesjokk og skraping og hadde en lav reaktivitet Gverfor metaller. The material according to the example had an excellent resistance to oxidation and corrosion and was resistant to heat shock and scratching and had a low reactivity to Gverfor metals.

Den usedvanlige kombinasjon av hoy fasthet og hoy hardhet sammen med de ovenfor angitte egenskaper gjor materialet ifolge eksemplet til et utmerket materiale for slitasjedeler, korrosjons- resistente deler og skjærende verktoy for maskinering av metaller. The extraordinary combination of high strength and high hardness together with the above-mentioned properties make the material according to the example an excellent material for wear parts, corrosion-resistant parts and cutting tools for machining metals.

Polerte prover av materialet kan også anvendes som smykkegjenstander. Polished samples of the material can also be used as jewelery items.

Eksempel 3 Example 3

Fremgangsmåten ifolge eksempel 1 ble gjentatt, men med den forandring at bestanddelene ble anvendt i slike mengder at det ble oppnådd et materiale inneholdende 50 volumprosent titannitrid, The procedure according to example 1 was repeated, but with the change that the components were used in such quantities that a material containing 50 volume percent titanium nitride was obtained,

36 volumprosent titancarbid, 7 volumprosent metallisk molybden og 36 volume percent titanium carbide, 7 volume percent metallic molybdenum and

7 volumprosent metallisk nikkel. 7 volume percent metallic nickel.

De virkelige mengder som ble fylt i 1,3 liters stålmollen, The actual quantities that were filled in the 1.3 liter steel mold,

var 81,^3 deler titannitridpulver, 53,32 deler titancarbidpulver, 21, ho deler metallisk molybdenpulver og 18,67 deler metallisk nikkelpulver. was 81.^3 parts titanium nitride powder, 53.32 parts titanium carbide powder, 21.ho parts metallic molybdenum powder and 18.67 parts metallic nickel powder.

Et presset råemne ble fremstilt ved varmpressing og undersokt som angitt i eksempel 1. A pressed blank was produced by hot pressing and examined as indicated in example 1.

Den gjennomsnittlige måo lte bbyningsfasthet var 21+lI+7 kg/cm<2>The average measured bending strength was 21+lI+7 kg/cm<2>

og den gjennomsnittlige Rockwell A hardhet 92,7. and the average Rockwell A hardness of 92.7.

Tettheten var 5,83 g/cm^ som tilsvarte den teoretiske tetthet. The density was 5.83 g/cm^ which corresponded to the theoretical density.

Materialet ifolge eksemplet hadde en utmerket- motstandsdyktighet overfor oxydasjon og korrosjon og var motstandsdyktig overfor varmesjokk og skraping og hadde lav reaktivitet overfor metaller. The material according to the example had excellent resistance to oxidation and corrosion and was resistant to thermal shock and scratching and had low reactivity to metals.

Den usedvanlige kombinasjon av hoy fasthet og hoy hardhet sammen med de ovenfor angitte egenskaper gjor at materialet ifolge eksemplet er et utmerket materiale for slitasjedeler, korrosjons-resistente deler og skjærende verktoy for maskinering av metaller. The extraordinary combination of high strength and high hardness together with the above-mentioned properties makes the material, according to the example, an excellent material for wear parts, corrosion-resistant parts and cutting tools for machining metals.

Eksempel h Example h

Fremgangsmåten ifolge eksempel 1 ble gjentatt, men med den forandring at bestanddelene ble anvendt i slike mengder at det ble oppnådd et materiale inneholdende *+5 volumprosent titancarbid, The procedure according to example 1 was repeated, but with the change that the components were used in such quantities that a material containing *+5 volume percent titanium carbide was obtained,

50 volumprosent titannitrid, 3 volumprosent metallisk molybden og 50 volume percent titanium nitride, 3 volume percent metallic molybdenum and

2 volumprosent metallisk nikkel. 2 volume percent metallic nickel.

De virkelige mengder som ble fylt i 1,3 liters stålmollen, The actual quantities that were filled in the 1.3 liter steel mold,

var 66,68 deler titancarbidpulver, 81,^-M- deler titannitridpulver, 9,17 deler metallisk molybdenpulver og 5,33 deler metallisk nikkel- was 66.68 parts titanium carbide powder, 81.^-M- parts titanium nitride powder, 9.17 parts metallic molybdenum powder and 5.33 parts metallic nickel-

pulver. powder.

Et presset råemne ble fremstilt ved varmpressing og under- A pressed blank was produced by hot pressing and sub-

sokt som angitt i eksempel 1. searched as indicated in example 1.

Den gjennomsnittlige målte boyningsfasthet var 18280 kg/cm<2>The average measured boying strength was 18280 kg/cm<2>

og den gjennomsnittlige Rockwell A hardhet 93,2. and the average Rockwell A hardness of 93.2.

Tettheten var 5,38 g/ cmJ som var over 99% av den teoretiske. The density was 5.38 g/cmJ which was over 99% of the theoretical.

Materialet ifolge eksemplet hadde en utmerket motstands- The material according to the example had an excellent resistance

dyktighet overfor oxydasjon og korrosjon og var motstandsdyktig overfor varmesjokk og. skraping og hadde lav reaktivitet overfor metaller. ability to oxidation and corrosion and was resistant to thermal shock and. scraping and had low reactivity towards metals.

Den usedvanlige kombinasjon av hby fasthet og hoy hardhet The extraordinary combination of high firmness and high hardness

sammen med de ovenfor angitte egenskaper gjor at materialet ifolge eksemplet er et utmerket materiale for slitasjedeler, korrosjons- together with the above-mentioned properties make the material, according to the example, an excellent material for wear parts, corrosion

resistente deler og skjærende verktoy for maskinering av metaller. resistant parts and cutting tools for machining metals.

Claims (5)

1. • Ildfast materiale inneholdende titannitrid og titancarbid som er bundet av en metallblanding som inneholder molybden,karakterisert vedat det består av<*>+9,5-9<*>+ volumprosent titannitrid, 5-<*>+9,5 volumprosent titancarbid og 1-15 volumprosent metall bestående i det vesentlige av 20-50 volumprosent nikkel og 50-8o volumprosent molybden, idet materialet har en tetthet over 99% av den teoretiske og en gjennomsnittlig kornstorrelse under 2 ym.1. • Refractory material containing titanium nitride and titanium carbide which is bound by a metal mixture containing molybdenum, characterized in that it consists of<*>+9.5-9<*>+ volume percent titanium nitride, 5-<*>+9.5 volume percent titanium carbide and 1-15 volume percent metal consisting essentially of 20-50 volume percent nickel and 50-80 volume percent molybdenum, the material having a density above 99% of the theoretical and an average grain size below 2 ym. 2. Materiale ifolge krav 1,karakterisert vedat dets gjennomsnittlige kornstorrelse er under 1 ym. 2. Material according to claim 1, characterized in that its average grain size is below 1 ym. 3. Materiale ifolge krav 1 eller 2,karakterisert ved at mengden av titancarbid i volumprosent er hbyere enn mengden av metall i volumprosent. k. 3. Material according to claim 1 or 2, characterized in that the quantity of titanium carbide in volume percentage is higher than the amount of metal in percent by volume. k. Materiale ifolge krav 1-3,karakterisert vedat'det består av 60-85 volumprosent titannitrid, 12-30 volumprosent titancarbid og 3-10 volumprosent metall. Material according to claims 1-3, characterized in that it consists of 60-85 volume percent titanium nitride, 12-30 volume percent titanium carbide and 3-10 volume percent metal. 5. Fremgangsmåte ved fremstilling av materialet ifolge krav 1-karakterisert vedat en homogen blanding av ^9,5-9'+ volumprosent titannitrid, 5-<*>+9,5 volumprosent titancarbid og 1-15 volumprosent metall bestående i det vesentlige av 20-50 volumprosent nikkel og 50-80 volumprosent molybden oppvarmes til en temperatur av 1600-1900°C, og at blandingen ved denne temperatur presses ved et trykk av 70,3-351,5 kg/cm 2, hvorpå det dannede press-stykke hurtig avkjoles.5. Process for the production of the material according to claim 1-characterized by a homogeneous mixture of ^9.5-9'+ volume percent titanium nitride, 5-<*>+9.5 volume percent titanium carbide and 1-15 volume percent metal consisting essentially of 20-50 volume percent nickel and 50-80 volume percent molybdenum is heated to a temperature of 1600-1900°C, and that the mixture at this temperature is pressed at a pressure of 70.3-351, 5 kg/cm 2 , after which the formed press piece is quickly cooled.
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US3971656A (en) * 1973-06-18 1976-07-27 Erwin Rudy Spinodal carbonitride alloys for tool and wear applications
US3994692A (en) * 1974-05-29 1976-11-30 Erwin Rudy Sintered carbonitride tool materials
US4049876A (en) * 1974-10-18 1977-09-20 Sumitomo Electric Industries, Ltd. Cemented carbonitride alloys
US4212670A (en) * 1978-03-13 1980-07-15 Alyamovsky Stanislav I Titanium oxycarbonitride based hard alloy
US4942097A (en) * 1987-10-14 1990-07-17 Kennametal Inc. Cermet cutting tool
GB2245557A (en) * 1990-06-27 1992-01-08 Johnson Matthey Plc Metal-ceramic composites
AR043243A1 (en) * 2003-02-24 2005-07-20 Shell Int Research CATALYST COMPOSITION, ITS PREPARATION AND USE
DK1794264T3 (en) * 2004-09-08 2020-08-24 Shell Int Research COMPOSITION OF HYDRO CRACKING CATALYST
JP5342740B2 (en) * 2005-09-27 2013-11-13 京セラ株式会社 Ceramics for decorative parts and decorative parts for watches using the same
US8083831B2 (en) * 2010-03-04 2011-12-27 Btr Limited Lightweight, anti-scratch and fracture resistant material for use in the manufacture of jewelry

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