SI8710868A8 - Procedure for making coherent fire resistant material on the surface and mixture of small parts for making such material - Google Patents
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Postopek za izdelavo koherentne žarovzdržne mase na površini in zmes delcev za izdelavo take maseA process for producing a coherent surface refractive mass and a mixture of particles to produce such mass
Področje tehnike, v katero spada izumFIELD OF THE INVENTION
MKP: F 27D 01/16IPC: F 27D 01/16
Predloženi izum je s področja metalurgije in se nanaša na postopek za izdelavo koherentne žarovzdržne masč na površini s tem, da proti tej površini brizgamo skupaj s kisikom, zmes žarovzdržnih delcev in goriva, ki reagira eksotermno z brizganim kisikom, da se sprosti zadostna toplota za staljenje vsaj površin žarovzdržnih * t . . t· delcev in se tako tvori žarovzdržna masa. Izum se nanaša tudi na zmes delcev za uporabo pri postopku izdelave koherentne žarovzdržne mase na površini z brizganjem proti tej površini zmesi in kisika, pri čemer ta zmes obsega žarovzdržne delce in delce goriva, ki so sposobni eksotermnega reagiranja s kisikom, da se sprostiThe present invention relates to the field of metallurgy and relates to a process for producing a coherent refractory grease on the surface by spraying with this surface together with oxygen, a mixture of refractory particles and fuel reacting exothermally with the injected oxygen to release sufficient heat for melt at least surfaces of refractory * t. . t · particles to form a refractory mass. The invention also relates to a mixture of particles for use in a method of producing a coherent refractory mass on a surface by spraying against this surface of a mixture and oxygen, wherein said mixture comprises refractory particles and fuel particles capable of exothermically reacting with oxygen to release
-'Ί .-'Ί.
έ. zadostna toplota za staljenje vsaj površin žarovzdržnih delcev, da se tvori žarovzdržna masa.έ. sufficient heat to melt at least the surfaces of the refractory particles to form a refractory mass.
Tehnični problemA technical problem
Obstajala je potreba, da bi izdelali koherentne, kompaktne (t.j. neporozne) žarovzdržne mase za oblaganje žarovzdržnih struktur za staljene kovinske materiale, pri čemer naj bi imele žarovzdržne mase enako ali podobno strukturo kot žarovzdržne strukture, ki vsebujejo ogljik, in naj bi se te mase dobro oprijele žarovzdržnih struktur. Stanje tehnike je zaželeno, da izdelamo žarovzdržno maso in situ na površini, lahko izbiramo med dvema tipoma znanega postopka.There was a need to produce coherent, compact (i.e., non-porous) refractory masses for coating refractory structures for molten metal materials, with refractory masses having the same or similar structure to carbon refractory structures. well-adhered to refractory structures. It is desirable for the prior art to produce a heat-resistant mass in situ on the surface, to choose between two types of known process.
Pri prvem tipu postopka, ki ga včasih označujejo kot “keramično varjenje” in je prikazan v GB-PS št. 1 330 894 (Glaverbel) in v britanski patentni prijavi, objavljeni pod št. GB 2 170 191 A (Glaverbel), izdelajo koherentno žarovzdržno maso na površini z brizganjem proti površini zmesi žarovzdržnih delcev in delcev goriva skupaj s kisikom. Uporabljeni delci goriva so delci s tako sestavo in granulometrijo, da eksotermno reagirajo s kisikom, posledica pa je tvorba žarovzdržnega oksid^ in sprostitev toplote, potrebne za staljenje vsaj površin brizganih žarovzdržnih delcev. Primera takih goriv sta aluminij in silicij. Ker se silicij obnaša kot nekatere kovine v tem, da se lahko močno eksotermno oksidira ob tvorbi žarovzdržnega oksida, čeprav priznavamo, da bi bilo treba silicij pravilno smatrati kot polkovino,je ugodno, da označujemo te gorivne elemente kjot kovinske. Na splošno je pri- 3 - poročljivo, da brizgajo delce v prisotnosti visoke koncentracije kisika, npr. ob uporabi kisika tržne kvalitete kot nosilnega plina. Na ta način lahko izdelajo koherentno žarovzdržno maso, ki se drži površine, proti kateri brizgajo delce. Zaradi zelo visokih temperatur v plamenu keramičnega varjenja plamen lahko največkrat prereže katerokoli žlindro, ki je lahko prisotna na površini žarovzdržnega materiala, ki ga obdelujemo, in zmehča ali stali to površino, tako da pride do dobrega spoja med površino, ki jo obdelujemo^ in na novo izdelano žarovzdržno maso.For the first type of process, sometimes referred to as "ceramic welding" and shown in GB-PS no. 1 330 894 (Glaverbel) and in British patent application published under no. GB 2 170 191 A (Glaverbel), produce a coherent refractory mass on the surface by spraying against the surface of a mixture of refractory and fuel particles together with oxygen. The fuel particles used are particles of such composition and granulometry that they react exothermically with oxygen, resulting in the formation of a refractory oxide ^ and the release of heat required to melt at least the surfaces of the injected refractory particles. Examples of such fuels are aluminum and silicon. Since silicon behaves like some metals in that it can be strongly exothermally oxidized upon the formation of refractory oxide, although it is recognized that silicon should be properly regarded as semi-metallic, it is advantageous to designate these Kyoto metal fuel elements. It is generally reported that they spray particles in the presence of high oxygen concentration, e.g. using marketable oxygen as a carrier gas. This way they can produce a coherent heat-resistant mass that adheres to the surface against which the particles are sprayed. Due to the very high temperatures in the ceramic welding flame, the flame can most often cut through any slag that may be present on the surface of the refractory material being machined and soften or stiffen this surface so that a good joint is formed between the machined surface ^ and at newly made heat-resistant mass.
Take znane postopke keramičnega varjenja lahko uporabljajo za izdelavo žarovzdržnega elementa, npr. bloka posebne oblike, vendar se najbolj običajno uporabljajo za izdelavo prevlek ali popravil na žarovzdržnih blokih ali stenah in so zlasti koristni za popravilo ali ojačanje obstoječih žarovzdržnih struktur, npr. za popravljanje sten ali prevlek sten peči za taljenje stekla, koksnih peči ali žarovzdržne opreme, ki se uporablja v metalurških industrijah.Such known ceramic welding processes can be used to produce a refractory element, e.g. special shape blocks, but are most commonly used for the manufacture of coatings or repairs on refractory blocks or walls and are particularly useful for repairing or reinforcing existing refractory structures, e.g. for repairing the walls or coatings of the walls of glass melting furnaces, coke ovens or refractory equipment used in the metallurgical industries.
Običajno izvedejo tako operacijo, ko je osnoven žarovzdržni material vroč, v nekaterih primerih pa je celo mogoče, da izvedejo popravilo ali ojačenje, ne da bi prekinili normalno delovanje opreme.They usually perform such an operation when the main refractory material is hot, and in some cases it may even be possible to perform repair or reinforcement without interrupting the normal operation of the equipment.
Jasno je, da učinkovito delovanje takih postopkov keramičnega varjenja zahteva hitro in popolno sproščanje toplote, ki se sprosti pri reakcijah med delci goriva in kisikom. Z drugimi besedami, zaželeno je, da bi vsi delci goriva popolnoma zgoreli, preden bi dosegli površino, ki jo napršujemo. Tudi visoka cena ustreznih delcev kovinskega _ /izgoriva spodbuja keramičnega varilca, da bi dobil največji dobitek, t.j. da dela tako, da je sežig goriva kar najbolj popolen in v izdelani žarovzdržni masi ni okludiranega preostalega nezgorelega goriva.It is clear that the effective operation of such ceramic welding processes requires the rapid and complete release of heat released by reactions between fuel particles and oxygen. In other words, it is desirable to burn all the fuel particles completely before reaching the sprayed surface. Also, the high cost of the corresponding metal _ / combustible particles encourages the ceramic welder to get maximum profit, i.e. that it works so that the combustion of the fuel is as complete as possible and that there is no residual unburned fuel in the produced refractory mass.
Drugi tip postopka za izdelavo žarovzdržne mase in situ na površini je znan kot plamensko naprševanje. Taki postopki obstoje v usmerjanju plamena na mesto, kjer je zaželeno, da se tvori žarovzdržna masa, in brizganju žarovzdržnega prahu preko plamena. Plamen se napaja s plinastim ali tekočim gorivom in včasih z uprašenim koksom. Jasno je, da učinkovito delovanje take tehnike plamenskega naprševanja zahteva popolen sežig goriva, da se ustvari kolikor je le mogoče vroč plamen in dobi maksimalen dobitek. Na splošno temperatura plamena, ki jo lahko dosežemo pri postopku plamenskega naprševanja, ni tako visoka, kot se jo lahko doseže pri tehniki keramičnega varjenja, rezultat pa je , da koherenca izdelane žarovzdržne mase ni tako velika ih ker se spoj med novo žarovzdržno maso in površino žarovzdržne osnove tvori pri nižji temperaturi, ni tako zanesljiv. Tak plamen je mnogo manj sposoben za prodiranje skozi katerokoli žlindro, ki je lahko prisotna na površini žarovzdržnega materiala, ki ga obdelujemo, kot je plamen pri postopku keramičnega varjenja.The second type of process for producing a heat-resistant mass in situ on a surface is known as flame spraying. Such processes exist in directing the flame to the location where it is desirable to form a heat-resistant mass and injecting heat-resistant dust over the flame. The flame is powered by gaseous or liquid fuel and sometimes by powdered coke. It is clear that the effective operation of such a flame spraying technique requires complete combustion of the fuel in order to generate as much hot flame as possible and obtain maximum yield. In general, the flame temperature achieved by the flame spray process is not as high as that achieved by the ceramic welding technique, and the result is that the coherence of the produced refractory mass is not as high as the junction between the new refractory mass and the surface forms a refractory base at a lower temperature, not so reliable. Such a flame is much less capable of penetrating any slag that may be present on the surface of the refractory material being treated, such as the flame in a ceramic welding process.
Tehniki keramičnega varjenja in plamenskega naprševanja, kot smo jih pravkar opisali, sta koristni za oblaganje ali popravilo sten ali prevlek, ki jih predstavljajo različni klasični žarovzdržni materiali, kot so bazični, kremenični, kremenično-glinični in cirkonijevi žarovzdržni materiali.Ceramic welding and flame spraying techniques, as just described, are useful for coating or repairing walls or coatings represented by various conventional refractory materials such as basic, quartz, quartz, alumina and refractory materials.
Sedaj v naraščajoči meri uporabljajo žarovzdržne ma teriale novega tipa, ki ga označuje visoka vsebnost ogljikovih delcev. Ti žarovzdržni materiali, ki vsebujejo ogljik, so običajno na osnovi magnezije ali glinice in lahko vsebujejo od 5 do 30 ali celo 35 mas.% ogljika. Take žarovzdržne materiale, ki vsebujejo ogljik, uporabljajo v industrijskih električnih talilnih pečeh in tudi v jeklarnah, v konvertorjih in izlivnih ponvah. Izbrani so zaradi visoke odpornosti proti eroziji in koroziji zaradi staljenih kovin in žlinder.They are now increasingly using new type refractory materials, characterized by high carbon content. These carbon-containing refractory materials are typically magnesium or alumina based and may contain from 5 to 30 or even 35% by weight of carbon. Such carbon-containing refractory materials are used in industrial electric melting furnaces and also in steel mills, converters and casting pans. They are selected for their high resistance to erosion and corrosion due to molten metals and slag.
Pri oblaganju ali ponovnem oblaganju žarovzdržne strukture je lahko zaželeno, da izdelajo žarovzdržno prevleko z boljšo obstojnostjo proti eroziji in koroziji, kot jo ima osnovni material. To pride zlasti v poštev pri delih žarovzdržne strukture, ki so zlasti podvrženi učinkom staljenega materiala, kot so izlivna ustja izlivnih ponev. Vendar je bolj običajno in, kadar se popravlja žarovzdržna struktura, prednostno, da izdelajo žarovzdržno maso, ki ima isto sestavo kot osnovni material. S tem se zagotovi, da je novi material kompatibilen z osnovnim materialom, na katerem se izdela, tako glede njegove kemične sestave kot tudi njegovih razteznih karakteristik. Če je med novim in starim žarovzdržnim maI terialom kemična ali fizikalna nekompatibilnost, je spoj med njima običajno slab ter se lahko obnovljeni del ali obloga odlušči.When coating or re-coating a heat-resistant structure, it may be desirable to produce a heat-resistant coating with better erosion and corrosion resistance than the base material. This is particularly relevant for parts of the refractory structure that are particularly susceptible to the effects of molten material, such as the outlet mouth of the outlet pan. However, it is more usual and, when repairing the heat-resistant structure, it is preferable to produce a heat-resistant mass having the same composition as the base material. This ensures that the new material is compatible with the base material on which it is made, both in terms of its chemical composition and its elongation characteristics. If there is a chemical or physical incompatibility between the new and the old refractory material, the joint between them is usually poor and the reconditioned part or liner may be ruled out.
Za izdelavo žarovzdržne mase, ki vsebuje ogljik, se zdi potrebno, da mora biti to pri temperaturi, ki ni previsoka, ali ob pogojih, ki niso ali so le rahlo oksidirajoči.In order to produce a carbon-containing refractory material, it seems necessary that this must be at a temperature that is not too high or under conditions that are not or only slightly oxidizing.
Tako se zdi primerno, da bi uporabili zgoraj opisano tehniko plamenskega naprševanja, pri čemer bi naprŠili zmes koksa in žarovzdržnih delcev ob takih pogojih, da za popolen sežig koksa ni zadosti kisika. Alternativna metoda bi bila uporaba paste z želeno sestavo in njen sežig v masi.Thus, it seems appropriate to use the flame-spraying technique described above, spraying a mixture of coke and refractory particles under such conditions that oxygen is not sufficient for complete combustion of the coke. An alternative method would be to use a paste of the desired composition and incinerate it in mass.
Opis rešitve tehničnega problema z izvedbenimi primeriDescription of solution to a technical problem with implementation examples
Presenetljivo pa smo ugotovili, da je mogoče izdelati žarovzdržne materiale, ki vsebujejo ogljik, z uporabo tehnike keramičnega varjenja, pri kateri žarovzdržni material in delce goriva brizgamo ob močno oksidacijskih pogojih, posledica pa je plamen z zelo visoko temperaturo. To je presenetljivo, ker bi normalno pričakovali, da bo istočasna prisotnost delcev ogljika in delcev kovinskega goriva v brizgani zmesi povzročila zgodnjo oksidacijo in izginotje delcev ogljika ob zakasnitvi oksidacije delcev goriva.Surprisingly, we have found that carbon-containing refractory materials can be manufactured using a ceramic welding technique whereby the refractory material and fuel particles are sprayed under highly oxidizing conditions and result in very high temperature flames. This is surprising because it would normally be expected that the simultaneous presence of carbon particles and metal fuel particles in the injected mixture would result in the early oxidation and disappearance of carbon particles upon delayed oxidation of the fuel particles.
V smislu predloženega izuma gre za postopek za izdelavo koherentne žarovzdržne mase na površini s tem, da proti tej površini brizgamo skupaj s kisikom zmes žarovzdržnih delcev in goriva, ki reagira eksotermno z brizganim kisikom, da se sprosti zadostna toplota za staljenje vsaj površin žarovzdržnih delcev in se tako tvori žarovzdržna masa, ki je fAccording to the present invention, it is a method of producing a coherent refractory mass on a surface by spraying together with oxygen a mixture of refractory particles and a fuel which reacts exothermally with the injected oxygen to release sufficient heat to melt at least the surfaces of refractory particles and thus a heat-resisting mass is formed which is f
označena s tem, da brizgana zmes vsebuje kot gorivo fino porazdeljene delce vsaj enega elementa, ki se da oksidirati v žarovzdržen oksid, in da brizgana zmes vsebuje tudi delce ogljika, ki so take velikosti ali sestave, da se delci ogljika okludirajo v izdelani žarovzdržni masi.characterized in that the injected mixture contains as a fuel finely divided particles of at least one oxidizable element, and that the injected mixture also contains carbon particles of a size or composition such that the carbon particles are occluded in the produced refractory mass .
Izraz delci ogljika, kot se tukaj uporablja, označuje delce, ki vsebujejo ogljik v elementarnem stanju ne glede na njegovo alotropsko obliko. Izraz delci, ki vsebujejo ogljik” označuje delce čistega ogljika in tudi delce ogljika, ki je pomešan ali kemično vezan z drugim materialom na tak način, da se delci lahko razkrojijo in pustijo ogljični ostanek.The term carbon particles, as used herein, means particles that contain carbon in the elemental state, regardless of its allotropic form. The term carbon-containing particles' means pure carbon particles as well as carbon particles mixed or chemically bound to other material in such a way that the particles can decompose and leave a carbon residue.
Učinkovitost postopka v smislu predloženega izuma je nepričakovana, ker je popolnoma v nasprotju s stanjem tehnike. Pri postopku v smislu predloženega izuma po eni strani delci goriva zgorijo v prisotnosti kisika s sproščanjem zadostne toplote za staljenje vsaj površin žarovzdržnih delcev, s katerimi so brizgani, medtem ko po drugi strani prečkajo deloi, ki vsebujejo ogljik, področje, kjer gori gorivo, ne da bi se oksidirali ali ne da bi se vsaj popolnoma oksidirali.The efficiency of the process of the present invention is unexpected because it is completely contrary to the state of the art. In the process of the present invention, on the one hand, the fuel particles burn in the presence of oxygen by releasing sufficient heat to melt at least the surfaces of the refractory particles with which they are sprayed, while on the other, the carbon-containing work crosses the fuel-burning area to oxidize or not at least completely oxidize.
Predloženi izum je zlasti koristen, ker omogoča izdelavo žarovzdržnih mas, ki so izredno odporne proti staljenim kovinam; omogoča popravilo ali oblaganje žarovzdržnih materialov ki vsebujejo ogljik, z žarovzdržnim materialom iste narave in omogoča, da na žarovzdržnem materialu, ki je manj odporen proti staljenim kovinam, nastane žarovzdržna masa, ki vsebuje ogljik.The present invention is particularly useful because it enables the manufacture of heat-resistant masses that are extremely resistant to molten metals; enables the repair or coating of carbon-containing refractory materials with a refractory material of the same nature, and allows the refractory material to be less resistant to molten metals to form a carbon-containing refractory mass.
Nadalje je prednost takega postopka enostavnost operacije ob uporabi naprave znanega tipa, kot se uporablja pri klasičnih postopkih keramičnega varjenja, omenjenih zgoraj v tem opisu.Furthermore, the advantage of such a process is the ease of operation using a device of the known type as used in the conventional ceramic welding processes mentioned above in this description.
Gorivo, ki ga je treba uporabiti, zajema delce vsaj enega elementa, ki se da oksidirati v žarovzdržen oksid. Na ta način lahko gorivo in žarovzdržne delce zmesi zlahka tako izberemo, da ima dobljena masa združenih delcevThe fuel to be used consists of particles of at least one oxidizable element in refractory oxide. In this way, the fuel and the refractory particles of the mixture can be easily selected so that the resulting mass of the combined particles
- 8 in proizvodov sežiga žarovzdržnih oksidov katerokoli želeno žarovzdržno sestavo, npr. v bistvu isto sestavo, kot je sestava žarovzdržne površine, proti kateri brizgamo zmes. Prednostno je, da so delci goriva delci silicija, aluminija in/ali magnezija. Delci teh elementov so tržno dostopni in jih lahko po potrobi mešamo v želenih razmerjih.- 8 and refractory oxide combustion products of any desired refractory composition, e.g. basically the same composition as the composition of the refractory surface against which the mixture is sprayed. Preferably, the fuel particles are particles of silicon, aluminum and / or magnesium. Particles of these elements are commercially available and can be mixed in desired proportions as needed.
Kot je znano, ima velikost delcev goriva važen vpliv na učinkovitost klasičnega postopka keramičnega varjenja. Pri klasičnih postopkih je zaželeno, da so delci goriva majhni, tako da hitro in popolnoma zgorijo med svojo trajektorijo rAs is well known, the size of the fuel particles has a significant impact on the efficiency of the classic ceramic welding process. For classic operations, it is desirable that the fuel particles be small so that they burn quickly and completely during their trajectory r
od kopja*, ki se uporablja za brizganje, do površine, ki jo obdelujemo. S tem dosežemo hitro sproščanje toplote in dobimo plamen z zelo visoko temperaturo, da dosežemo zadovoljivo staljenje žarovzdržnih delcev in tako dobimo koherentno in kompaktno žarovzdržno maso. Presenetljivo smo ugotovili, da je pri postopku v smislu predloženega izuma priporočljiva podobna granulometrija goriva. Tako naj bi imeli delci goriva za najboljše rezultate srednjo velikost zrn pod 50 pm. Dejansko je za delce goriva zaželeno, da imajo tako granulometrijo, da jih ima vsaj 90 mas.% velikost zrn pod 50 pm. Posebno primerni so delci s srednjo velikostjo zrn v območju 5 pm do 20 pmfrom the spear * used for injection molding to the surface being machined. This achieves rapid heat release and produces a very high temperature flame to achieve a satisfactory melt of the refractory particles to produce a coherent and compact refractory mass. Surprisingly, we found that similar fuel granulometry is recommended in the process of the present invention. Thus, for best results, the fuel particles should have a mean grain size below 50 pm. In fact, it is desirable for the fuel particles to have a granulometry such that at least 90% by weight of the grain size is below 50 pm. Particles with a medium grain size in the range of 5 pm to 20 pm are particularly suitable
Delce, ki vsebujejo ogljik, lahko oblikujemo iz materiala, ki je poceni in zlahka dostopen. Med materiali, ki so primerni, lahko navedemo premog, koks, lignit, oglje, grafit, karbonska vlakna, izrabljene elektrode peči in organske materiale, kot sladkorje in sintetske smole. Trenutno je zlasti prednostna uporaba delcev polimernega materiala, ker jih zlahka predelamo pred brizganjem v zmesi in zlasti zaradiCarbon-containing particles can be formed from a material that is inexpensive and easily accessible. Suitable materials include coal, coke, lignite, charcoal, graphite, carbon fibers, spent furnace electrodes, and organic materials such as sugars and synthetic resins. At present, the use of polymeric material particles is particularly preferred because they are easily processed before injection into the mixture and especially because
- 9 enostavnosti, s katero lahko polimerne materiale oblikujemo v delce z želeno granulometrijo. Delce, ki vsebujejo ogljik, za uporabo pri izumu lahko tudi izdelamo z nanašanjem polimernega prešlojevanja na žarovzdržne delce.- 9 ease with which polymeric materials can be molded into particles with the desired granulometry. Carbon-containing particles for use in the invention can also be made by applying a polymer coating to the refractory particles.
Mogoče je, da se zanesemo le na velikost delcev, ki vsebujejo ogljik, da se prepreči njihov kompleten sežig med brizganjem, tako da so delci ogljika okludirani v izdelani žarovzdržni masi. Zunanja lupina delca lahko zgori, da dobimo ogljikovo jedro, ki se okludira v žarovzdržnem materialu.It may be necessary to rely solely on the size of the carbon-containing particles to prevent their complete combustion during injection, so that the carbon particles are occluded in the produced refractory mass. The outer shell of the particle can burn to produce a carbon core that occludes in the refractory.
Če je treba to storiti, je prednostno, da imajo delci, ki vsebujejo ogljik, povprečno velikost zrn nad 0,5 mm.If this is to be done, it is preferred that the carbon-containing particles have an average grain size above 0.5 mm.
Vendar je prednostno, da se zanesemo na sestavo delcev, ki vsebujejo ogljik, prednostno pa ti delci, ki vsebujejo ogljik, obsegajo delce, ki so sestavljeni iz jedra iz materiala, ki vsebuje ogljik, ki je pokrito s plaščem materiala, ki preprečuje oksidacijo takega jedra. To olajša tvorbo žarovzdržne mase z okludiranimi delci ogljika. Na ta način se zlasti poveča kontrola količine ogljika, ki se tako okludira. Če material plašča prepreči oksidacijo jedra, ki vsebuje ogljik, potem sledi, da bo ves ogljik, ki ga vsebuje jedro, okludiran, kar pomeni, da lahko z gotovostjo izdelamo žarovzdržen material, ki vsebuje ogljik, z dano vsebnostjo okludiranega ogljika iz brizgane zmesi delcev z dano sestavo.However, it is preferable to rely on the composition of the carbon-containing particles, and preferably those carbon-containing particles comprise particles consisting of a core of carbon-coated material that is coated with a material that prevents oxidation of such sails. This facilitates the formation of a heat-resistant mass with occluded carbon particles. This in particular increases the control of the amount of carbon thus occluded. If the mantle material prevents the oxidation of the core containing carbon, then it follows that all the carbon contained in the core will be occluded, which means that a refractory carbon-containing material with a given content of occluded carbon from the injected particulate mixture can be produced with certainty. with a given composition.
Doslej smo omenjali okludiranje le delcev ogljika v žarovzdržni masi za izdelavo žarovzdržne mase, ki vsebuje ogljik. V sedanji industrijski praksi pa je tudi narasla uporaba žarovzdržnih materialov, ki vsebujejo ogljik in ki vsebu10 jejo okludirane delce elementa, ki se da oksidirati v žarovzdržni oksid. Posebni primeri takih elementov so silicij, magnezij, cirkonij in aluminij. Namen vključevanja teh elementov je zmanjšanje difuzije kisika,'Skozi žarovzdržen; material in tako izboljšanje obnašanja žarovzdržnega telesa. Katerikoli kisik, ki difundira v žarovzdržen material, se običajno združi s takimi elementarnimi delci, ker pa je rezultat takega združenja žarovzdržen oksid, struktura žarovzdržnega materiala ni zelo oslabljena zaradi pojava npr. vrzeli. Ker se Silicij obnaša kot nekatere kovine tudi v tem pogledu, je ugodno, da označimo žarovzdržne materiale, v katerih so okludirani taki delci, z izrazom ki vsebuje kovino.So far, we have mentioned the occlusion of only carbon particles in the refractory mass to produce a refractory carbon-containing mass. In the current industrial practice, however, the use of carbon-containing refractory materials which contain occluded particles of an oxidizable element in refractory oxide has also increased. Specific examples of such elements are silicon, magnesium, zirconium and aluminum. The purpose of incorporating these elements is to reduce the diffusion of oxygen, 'Through refractory; material and thus improve the behavior of the refractory body. Any oxygen that diffuses into a refractory material is usually combined with such elemental particles, but since the result of such an association is a refractory oxide, the structure of the refractory material is not very weakened by the appearance of e.g. gaps. Since Silicon behaves like some metals in this respect, it is advantageous to label the refractory materials in which such particles are occluded by the term metal.
Kot velja za žarovzdržne materiale, ki vsebujejo ogljik, je zaželeno, da bi lahko in situ izvedli vroče popravilo ali ojačenje žarovzdržnih materialov, ki vsebujejo kovino.As is the case for carbon-containing refractory materials, it is desirable to allow hot repair or reinforcement of refractory metal-containing materials in situ.
Kot bomo omenili, vključujejo ti kovinski elementi elemente, katerih uporaba je zlasti priporočljiva v delcih goriva za uporabo v postopku keramičnega varjenja. Presenetljivo smo ugotovili, da je mogoče ob določenih pogojih uporabiti postopek keramičnega varjenja za izdelavo žarovzdržne mase, ki vsebuje ogljik in ki vsebuje okludirane kovinske delce.As will be mentioned, these metallic elements include elements whose use is particularly recommended in fuel particles for use in the ceramic welding process. Surprisingly, it has been found that, under certain conditions, a ceramic welding process can be used to produce a carbon-containing refractory containing occluded metal particles.
Torej gre pri določenih prednostnih izvedbah v smislu predloženega izuma za to, da brizgana zmes nadalje vsebuje delce, ki obsegajo vsaj en element, ki se da oksidirati v žarovzdržen oksid,ti delci pa so take velikosti ali sestave, da delci takega elementa postanejo okludirani v izdelani žarovzdržni masi.Thus, in certain preferred embodiments of the present invention, the injected mixture further comprises particles comprising at least one element which can be oxidized to refractory oxide, and these particles are of such size or composition that the particles of such element become occluded in the made heat-resistant masses.
Izbira kovinskega elementa (kovinskih elementov) za tChoosing a metal element (s) for t
vdei&vo v take nadaljnje delce je odvisna od sestave žarovzdržne matrice, v kateri naj bi se okludirali, in od zahtevanih lastnosti žarovzdržne mase pred, med in po katerikoli oksidaciji takih delcev. Na splošno je prednostno, da taki nadaljnji delci obsegajo vsaj en element izmed silicija, magnezija, cirkonija in aluminija.the incorporation into such further particles depends on the composition of the refractory matrix in which they are to be occluded and on the required properties of the refractory mass before, during and after any oxidation of such particles. It is generally preferred that such further particles comprise at least one element of silicon, magnesium, zirconium and aluminum.
Prednostno je, da taki nadaljnji delci obsegajo delce, ki so sestavljeni iz jedra iz vsaj enega tega elementa, ki se. da oksidirati v f žarov zdi;Ž,£n oksid, to jedro pa je pokrito s plaščem materiala, ki preprečuje oksidacijo takega jedra. S tem je omogočena boljša kontrola in *ftftafmjfrjfe določitev količine takega elementa jedra, ki bo okludiran v izdelani žarovzdržni masi, kot je to mogoče, če se enostavno zanesemo na velikost nadaljnjih delcev.Preferably, such further particles comprise particles consisting of a core of at least one of these elements, which. to oxidize to f gels seems; Ž, £ n oxide, and this nucleus is covered by a sheath of material which prevents the oxidation of such a nucleus. This enables better control and * ftftafmjfrjfe determination of the amount of such core element that will be occluded in the produced refractory mass than is possible if one can simply rely on the size of further particles.
Plašče, ki pokrivajo jedra, ki vsebujejo ogljik, in plašče, ki pokrivajo kovinska jedra, lahko ugodno izberemo iz istih razredov materialov. Zaželeno je, da izberemo anorganski material, ki je v bistvu inertčnh glede na kisik, tako da učinkovito preprečuje oksidacijo materiala jedra, in ki ne bo povzročil napak v izdelani žarovzdržni masi. To omogoča uporabo delcev z jedri, ki vsebujejo ogljik, ali kovinskimi jedri, katerih vsebnost ogljika in,če se uporabi , kovinska vsebnost natančno ustreza količini ogljikovih ali kovinskih delcev, ki naj bi se okludirali v žarovzdržnem materialu, in s tem se izognemo potrebi po uporabi materialov, katerih reakcije bi lahko|nezanesljivo ali težko kvantitativno kontrolirali med brizganjem. Zato prednostno material plašča obsega enega ali več kovinskih oksidov, nitridov ali karbidov in ugodno plašči obsegajo enega ali več oksidov, nitridov ali karbidov magnezija, aluminija, silicija, titana, cirkonija ali kroma. Take spojine lahko s precejšnjo lahkoto nanesemo na trdne delce in imajo žarovzdržen karakter, ki je kompatibilen z žarovzdržno maso, ki se bo tvorila v postopku.Coats that cover carbon cores and coats that cover metal cores can be conveniently selected from the same material classes. It is desirable to select an inorganic material which is substantially inert with respect to oxygen so as to effectively prevent the oxidation of the core material, and which will not cause defects in the refractory mass produced. This allows the use of particles with carbon-containing cores or metal cores whose carbon content and, if used, the metal content exactly corresponds to the amount of carbon or metal particles that are to be occluded in the refractory material, thereby avoiding the need for the use of materials whose reactions | could be unreliably or difficult to quantitatively control during injection. Therefore, the coating material preferably comprises one or more metal oxides, nitrides or carbides, and preferably the coatings comprise one or more oxides, nitrides or carbides of magnesium, aluminum, silicon, titanium, zirconium or chromium. Such compounds can be applied to solids with considerable ease and have a refractory character that is compatible with the refractory mass that will be formed in the process.
Plašč lahko oblikujemo kot kontinuirno prevleko, ki popolnoma obdaja jedro kot jajčna lupina, ali pa se lahko, zlasti če je jedro porozno, absorbira ali adsorbira kot površinska prevleka na jedru. V kateremkoli primeru plašč ščiti jedro, bodisi iz materiala, ki vsebuje ogljik, ali kovinskega materiala, proti oksidaciji.The mantle can be formed as a continuous coating that completely encloses the nucleus as an egg shell, or, especially if the nucleus is porous, can be absorbed or adsorbed as a surface coating on the nucleus. In either case, the jacket protects the core, either of carbon-containing material or metallic material, against oxidation.
Pri nekaterih prednostnih izvedbah izuma kovinski oksid, nitrid ali karbid nanesemo pod vakuumom. To lahko izvedemo z uparjanjem kovinskega materiala, ki ga nato spojimo s kisikom, dušikom ali ogljikom, da dobimo ustrezen oksid, nitrid ali karbid.In some preferred embodiments of the invention, the metal oxide, nitride or carbide is applied under vacuum. This can be done by evaporating the metal material, which is then combined with oxygen, nitrogen or carbon to give the corresponding oxide, nitride or carbide.
Pri drugih prednostnih izvedbah izuma kovinski oksid nitrid ali karbid nanesemo tako, da spravimo delce materiala jedra v stik z reaktivno tekočino in jih nato segrevamo. Na ta način lahko jedra, ki jih je treba zaščititi, z lahkoto pomešamo z enim ali več reagenti, npr. z eno ali več organokovinskimi spojinami, ki je ali so tekoče ali v raztopini, in nato zadosti segrevamo, da izženemo katerokoli prisotno topilo, in reagent (reagente) piroliziramo, da dobimo plašče. Tak postopek lahko ugodno uporabimo za nanašanje enega ali več oksidov na delce, ki vsebujejo ogljik, s segrevanjem do temperature okoli 500 °C.In other preferred embodiments of the invention, the metal oxide nitride or carbide is applied by contacting particles of the core material with the reactive liquid and then heating them. In this way, the cores to be protected can be easily mixed with one or more reagents, e.g. with one or more organometallic compounds, which are either liquid or in solution, and then sufficiently heated to expel any solvent present, and the reagent (s) pyrolyzed to give the coats. Such a process can advantageously be applied to the deposition of one or more oxides on carbon-containing particles by heating to a temperature of about 500 ° C.
Pri še drugih prednostnih izvedbah izuma za izdelavo žarovzdržnih materialov, ki vsebujejo kovino, delce jedra vsaj enega elementa, ki se da oksidirati v žarovzdržen oksid, površinsko oksidiramo, da dobimo oksidni plašč, s tem, da jih izpostavimo toploti in kisiku v fluidizirani blazini.In other preferred embodiments of the invention for the manufacture of refractory materials containing metal, the core particles of at least one oxidizable element in the refractory oxide are surface oxidized to form an oxide mantle by subjecting them to heat and oxygen in a fluidized bed.
To je posebno ugoden način zaščite takih jeder delcev proti oksidaciji med brizganjem.This is a particularly advantageous way of protecting such particle nuclei against oxidation during injection molding.
Prednostno delce jedra vzdržujemo v gibanju med nanašanjem kovinskega oksida, nitrida ali karbida. S tem je omogočena enotna istočasna obdelava velikega števila jeder delcev. Jedra delcev lahko mehansko mešamo med preslojevanjem pod vakuumom ali ko so v stiku z reaktivno tekočino.Preferably, the core particles are maintained in motion during the deposition of metal oxide, nitride or carbide. This enables uniform processing of a large number of particle nuclei simultaneously. The particle nuclei can be mechanically stirred during the coating under vacuum or when in contact with the reactive fluid.
Po drugi strani lahko jedra delcev obdelujemo s plinastim reagentom po tehniki fluidizirane blazine.On the other hand, particle nuclei can be treated with a gaseous reagent according to the fluidized bed technique.
V nasprotju s tem, kar bi lahko pričakovali, učinkovitost postopka v smislu predloženega izuma ni odvisna od izvajanja v okolju, ki ima precej nizko vsebnost kisika.Contrary to what you might expect, the efficiency of the process of the present invention is not dependent on being performed in an environment that has a relatively low oxygen content.
Mogoče je in dejansko je priporočljivo, da brizgamo zmes delcev ob pogojih, ki so ugodni za popolno eksotermno oksidacijo delcev goriva, in temu ustrezno je prednostno, da kisik predstavlja vsaj 60 vol.% plina, ki ga brizgamo proti tej površini.It is possible and indeed advisable to spray the particulate mixture under conditions that are conducive to complete exothermic oxidation of the fuel particles and, accordingly, it is preferable that oxygen represents at least 60% by volume of the gas sprayed against this surface.
Zmes delcev za uporabo pri postopku v smislu predloženega izuma, kot je zgoraj opisan, ima sama po sebi določene prednosti in pri predloženem izumu gre tudi za zmes delcev za uporabo pri postopku za izdelavo koherentne žarovzdržne mase na površini s tem, da proti tej površini brizgamo zmes in kisik, pri čemer zmes obsega žarovzdržne delce in delce goriva, ki so sposobni eksotermne reakcije s kisikom, da se sprosti zadostna toplota za staljenje vsaj površin žarovzdržnih delcev za izdelavo žarovzdržne mase, označena s tem, da zmes vsebuje kot gorivo fino porazdeljene delce s srednjo velikostjo zrn pod 50 pm vsaj enega elementa, ki se da oksidirati v žarovzdržen oksid, in da zmes tudi vsebuje delce, ki vsebujejo ogljik, s tako velikostjo ali sestavo, da v primeru, ko zmes brizgamo proti površini v prisotnosti kisika ob pogojih, ki vodijo do v bistvu popolne oksidacije del cev goriva in nastanka koherentne žarovzdržne mase, delci ogljika niso popolnoma oksidirani, pri čemer delci ogljika postanejo okludirani v nastali žarovzdržni masi.The particulate mixture for use in the process of the present invention, as described above, has certain advantages in itself and the present invention is also a mixture of particles for use in a method for producing a coherent heat-resistant mass on a surface by spraying against that surface the mixture and oxygen, the mixture comprising refractory particles and fuel particles capable of exothermic oxygen reaction to release sufficient heat to melt at least the surfaces of the refractory particles to produce a refractory mass, characterized in that the mixture contains finely divided particles as a fuel having a mean grain size below 50 pm of at least one oxidizable element in the refractory oxide and that the mixture also contains carbon-containing particles of such size or composition that when the mixture is sprayed to the surface in the presence of oxygen under conditions leading to essentially complete oxidation of the fuel pipe and the formation of a coherent refractory mass, the carbon particles are not completely oxidized, at causing the carbon particles to become occluded in the resulting refractory mass.
Taka zmes delcev omogoča izdelavo žarovzdržnih mas, ki vsebujejo ogljik, z visoko obstojnostjo proti koroziji in eroziji zaradi staljenih kovin, ki so sposobne ohraniti tako visoko obstojnost ves čas uporabe. Z uporabo take zmesi, npr. pri postopku keramičnega varjenja, lahko zlahka izdelamo kompaktne žarovzdržne mase, ki se lahko dobro oprimejo mnogih žarovzdržnih površin. Ker zmes zajema delce goriva, ka terih srednja velikost zrn je pod 50 pm (in ki imajo prednost no največjo velikost, ki ne preseže 50 pm), se pospeši popolna reakcija delcev goriva. Taki delci hitro reagirajo s kisikom, hitro sprostijo toploto, potrebno za nastanek kompaktne žarovzdržne mase na površini, na katero brizgamo zmes. Tako zmes lahko dobimo brez težav s pomešanjem delcev, ki so tržno dostopni ali ki jih lahko specialno izdelamo, vendar iz primarnih materialov, ki so zlahka dostopni.Such a mixture of particles enables the production of carbon-containing refractory materials with high corrosion and erosion resistance due to molten metals capable of maintaining such high durability throughout use. By using such a mixture, e.g. In the process of ceramic welding, compact refractory masses can be easily produced that can hold well on many refractory surfaces. Since the mixture comprises fuel particles with a mean grain size of less than 50 µm (and preferably a maximum size not exceeding 50 µm), the complete reaction of the fuel particles is accelerated. Such particles react quickly with oxygen, quickly releasing the heat required to form a compact heat-resistant mass on the surface on which the mixture is sprayed. Such a mixture can be easily obtained by mixing particles that are commercially available or that can be specially made, but from primary materials that are readily available.
Žarovzdržni delci zmesi imajo lahko kakršnokoli želeno sestavo.Lahko so npr. delci enega ali več materialov, izbranih izmed silimanita, mulita, cirkona, kremena, cirkonije in glinice. Zmes lahko pri tem prilagodimo za izdelavo žarovzdržne mase, ki vsebuje ogljik in ki ima sestavo, ki ustreza enemu izmed številnih običajnih žarovzdržnih pripravkov. Zlasti je prednostno, da so ti žarovzdržni delci vsaj v glavnem delci magnezijevega oksida, tako da je omogočena izdelava bazičnih žarovzdržnih mas, ki so kompatibilne z večino žarovzdržne opreme, ki se uporablja v stiku s staljenimi kovinami.The refractory particles of the mixture may have any desired composition. particles of one or more materials selected from silymanite, mullite, zircon, quartz, zirconia and alumina. The mixture can then be adapted to produce a carbon-containing heat-resistant mass having a composition corresponding to one of many conventional heat-resistant preparations. In particular, it is preferred that these refractory particles are at least principally magnesium oxide particles, so that basic refractory masses that are compatible with most of the refractory equipment used in contact with molten metals are made.
Za izhodne materiale, ki vsebujejo ogljik, ni nujno, da so čisti ogljik, ampak lahko, kot je povedano zgoraj, vsebujejo ogljik pomešan ali kemično vezan z drugimi elementi.Carbon-containing starting materials need not be pure carbon, but as mentioned above may contain carbon mixed or chemically bonded with other elements.
Tako lahko izberemo premog, grafit, lignit, koks, oglje, karbonska vlakna, ostanke elektrod iz električnih peči, itd., sintetske smole, organske materiale, kot sladkorje, itd. Sedaj je zlasti prednostna uporaba delcev polimernega materiala zaradi njihove lahke predelave pred brizganjem v zmesi, zlasti pa zaradi lahkote, s katero lahko polimerne materiale oblikujemo v delce z želeno granulometrijo. Kot je bilo omenjeno, lahko delce, ki vsebujejo ogljik, za uporabo v izumu tudi izdelamo z nanašanjem polimerne prevleke na žarovzdržne delce.Thus, coal, graphite, lignite, coke, charcoal, carbon fiber, electrode residues from electric furnaces, etc., synthetic resins, organic materials such as sugars, etc. can be selected. It is now particularly advantageous to use particles of polymeric material because of their easy processing before injection into the mixture, and especially because of the ease with which the polymeric materials can be formed into particles with the desired granulometry. As mentioned, carbon-containing particles for use in the invention can also be made by applying a polymer coating to refractory particles.
V skladu z nekaterimi prednostnimi izvedbami zmesi v smislu izuma imajo ti delci, ki vsebujejo ogljik, srednjo velikost zrn nad 0,5 mm. Take delce zlahka pripravimo iz mletih in presejanih materialov, ki vsebujejo ogljik. Delcev, ki imajo srednji premer nad 0,5 mm, ni potrebno posebej obdelati, da bi bili relativno ali popolnoma nereaktivni proti kisiku. Nasprotno, mogoče je, da se ti delci površinsko oksidirajo, pri čemer obdržijo ali tvorijo jedro ogljika, ki ostane v žarovzdržni masi,izdelani z brizganjem te zmesi v kisiku. Za izdelavo žarovzdržne mase, ki vsebuje ogljik in ki vsebuje delce ogljika z danim srednjim premerom, je priporoč ljivo, da izberemo izhodno zmes, ki obsega delce, ki vsebujejo ogljik, katerih srednji premer je vsaj dvakrat večji od danega premera.According to some preferred embodiments of the compositions according to the invention, these carbon-containing particles have a mean grain size greater than 0.5 mm. Such particles are readily prepared from ground and sieved carbon-containing materials. Particles having a mean diameter greater than 0.5 mm need not be specially treated to be relatively or completely non-reactive to oxygen. On the contrary, it is possible for these particles to surface oxidize, retaining or forming a carbon core that remains in the refractory mass produced by spraying this mixture in oxygen. In order to produce a carbon-containing refractory mass containing carbon particles of a given mean diameter, it is advisable to select an initial mixture comprising carbon-containing particles whose mean diameter is at least twice the diameter given.
Vendar je prednostno, da imajo ti delci, ki vsebujejo ogljik, delce, ki so sestavljeni iz jedra materiala, ki vsebuje ogljik, ki je pokrito s plaščem materiala, ki v primeru, kadar zmes brizgamo proti tej površini v prisotnosti kisika, in ob pogojih, ki vodijo do praktično popolne oksidacije teh delcev goriva in izdelave koherentne žarovzdržne mase, inhibira oksidacijo takega jedra. Delce te vrste lahko držimo, skladiščimo in obdelujemo v atmosferi, ki vsebuje kisik, brez posebnih varnostnih ukrepov. To tudi zelo olajša napoved velikosti zrn delcev ogljika, ki se bodo okludirali v žarovzdržni masi, ki vsebuje ogljik in ki jo izdelamo z brizganjem zmesi ob teh pogojih, in tako olajša zanesljivo izdelavo žarovzdržne mase z, zaželeno sestavo iz zmesi s predhodno določenimi razmerji njenih različnih sestavin.However, it is preferable that these carbon-containing particles have particles consisting of a core of carbon-coated material that is coated with a material that, when the mixture is sprayed against this surface in the presence of oxygen, and under conditions , which lead to the virtually complete oxidation of these fuel particles and the production of a coherent refractory mass, inhibits the oxidation of such a nucleus. Particles of this type can be held, stored and treated in an oxygen-containing atmosphere without special precautions. This also greatly facilitates the prediction of the grain size of the carbon particles that will occlude in the carbon-containing refractory mass produced by injection molding the mixture under these conditions, thus facilitating the reliable fabrication of the refractory mass with the desired composition from the mixture with predetermined ratios of its different ingredients.
Pri nekaterih prednostnih izvedbah zmesi v smislu izuma zmes nadalje vsebuje delce, ki vsebujejo vsaj en element ki se da oksidirati v žarovzdržen oksid, ti nadaljnji delci pa imajo tako velikost ali sestavo, da se v primeru, ko zmes brizgamo proti tej površini v prisotnosti kisika in ob pogojih, ki vodijo do praktično popolne oksidacije teh delcev goriva in izdelave koherentne žarovzdržne mase, ne bodo popolnoma oksidirali, pri čemer so delci takega elementa (takih elementov) okludirani v izdelani žarovzdržni masi.In some preferred embodiments, the composition according to the invention further comprises particles containing at least one oxidizable element in refractory oxide, and these further particles are of such size or composition that when the mixture is sprayed against this surface in the presence of oxygen and under conditions that lead to the virtually complete oxidation of these fuel particles and the production of a coherent refractory mass, they will not be completely oxidized, leaving the particles of such element (s) in the refractory mass produced.
Okludiran material te vrste podeli žarovzdržnim masam, izdelanim iz zmesi, povečano obstojnost proti koroziji.The occluded material of this type confers increased resistance to corrosion to the heat-resistant masses made of the mixture.
Zmesi te vrste lahko tudi izdelamo brez težav. Zmesi te vrste lahko izdelamo ob uporabi tržno dostopnih kovinskih praškov.Mixtures of this kind can also be made easily. Mixtures of this kind can be made using commercially available metal powders.
Prednostno je v takih nadaljnjih delcih prisoten vsaj en element, izbran izmed silicija, magnezija, cirkonija in aluminija. Ugodno taki nadaljnji delci obsegajo jedro iz vsaj enega od teh elementov, ki se da oksidirati v žarovzdržen oksid, ki je pokrito s plaščem materiala, ki ob teh pogojih preprečuje oksidacijo jedra.Preferably, at least one element selected from silicon, magnesium, zirconium and aluminum is present in such further particles. Advantageously, such further particles comprise a core of at least one of these elements that can be oxidized to a refractory oxide covered with a sheath of material that prevents oxidation of the core under these conditions.
Prednostno material plašča obsega enega ali več kovinskih oksidov, nitridov ali karbidov, prednostno pa plašči obsegajo enega ali več oksidov, nitridov ali karbidov magnezija, aluminija, silicija, titana, cirkonija ali kroma.Preferably, the jacket material comprises one or more metal oxides, nitrides or carbides, and preferably the jackets comprise one or more oxides, nitrides or carbides of magnesium, aluminum, silicon, titanium, zirconium or chromium.
Take spojine se nanesejo na jedra delcev brez težav, ne da bi po nepotrebnem povečali njihovo ceno. Lahko tvorijo sloj okoli jedra in tako oblikujejo lupino ali pa lahko po drugi strani impregnirajo površinske sloje jedra, če je porozno.Such compounds are applied to particle nuclei without difficulty, without unnecessarily increasing their cost. They can form a layer around the nucleus and thus form a shell or, on the other hand, impregnate the surface layers of the nucleus if it is porous.
Nanos te vrste lahko izdelamo na jedrih npr. z vakuumskim uparjenjem kovine, ki mu nato sledi njeno spajanje s kisikom, dušikom ali ogljikom, ali z nanašanjem organokovinskega predhodnika, ki se pretvori v oksid pri zmerni temperaturi. Delce te vrste pred vdelavo v zmes posebej pripravimo, vendar se čas ali stroški, potrebni za to pripravo, kar v največji meri kompenzirajo z varnostjo uporabe zmesi in napovedljivostjo rezultatov, ko zmes uporabimo pri postopku keramičnega varjenja.Application of this type can be made on cores e.g. by vacuum evaporation of the metal, followed by its coupling with oxygen, nitrogen or carbon, or by deposition of an organometallic precursor, which is converted to the oxide at a moderate temperature. Particles of this type are specially prepared prior to incorporation into the mixture, but the time or cost required for this preparation is largely offset by the safety of use of the mixture and the predictability of results when the mixture is used in the ceramic welding process.
Za zaščito jeder delcev proti oksidaciji z zadovoljivo varnostno stopnjo material teh plaščev prednostno pred stavlja od 0,02 do 2 mas.% delcev, skupaj applaščiriThka« Ts<a količina plaščnega materiala omogoča tvorbo popolnih slojev okoli teh delcev. Da bi omogočili izdelavo žarovzdržnih mas s sestavo, ki je podobna sestavi tržno dostopnih žarovzdržnih mas, ki vsebujejo ogljik in ki v danem primeru vsebujejo tudi kovine, je prednostno, da so delci, ki vsebujejo ogljik, in v danem primeru nadaljnji delci prisotni v celotni količini od 2 do 50 mas.% zmesi. Prednostno je količina delcev, ki vsebujejo ogljik, med 5 in 50 % in količina v danem primeru prisotnih nadaljnjih delcev med 2 in 10 %. Prisotnost takih količin v zmesi zagotavlja, da s pomočjo brizganja v prisotnosti kisika izdelamo žarovzdržne mase, ki vsebujejo zadosti ogljika, kjer je primerno , zadosti okludirane kovine, ki podeli masam visoko obstojnost proti koroziji in eroziji zaradi staljenih materialov pri zvišani temperaturi.In order to protect the particle nuclei against oxidation with a satisfactory safety degree, the material of these coats preferably comprises from 0.02 to 2% by weight of the particles, together applauding a Thin «Ts <a quantity of the coating material allows the formation of complete layers around these particles. In order to enable the production of refractory masses with a composition similar to that of commercially available refractory carbon-containing masses, which optionally include metals, it is preferable that carbon-containing particles and, in the present case, further particles be present throughout in an amount of from 2 to 50% by weight of the mixture. Preferably, the amount of carbon-containing particles is between 5 and 50% and the amount of further particulate matter present is between 2 and 10%, as appropriate. The presence of such quantities in the mixture ensures that refractory masses containing sufficient carbon, where appropriate, sufficiently occlude the metal to be produced by injection molding in the presence of oxygen, which give the masses a high resistance to corrosion and erosion by molten materials at elevated temperatures.
Tako iz gospodarskih kot tudi iz tehničnih razlogov zmes prednostno vsebuje delce goriva v razmerju 5 do 30 mas.%. Taka količina uporabljenega tipa goriva je zadostna, da se žarovzdržni delci, ki ga spremljajo, ko zmes brizgamo v prisotnosti kisika, vsaj površinsko stalijo.For economic as well as technical reasons, the mixture preferably contains fuel particles in the ratio of 5 to 30% by weight. Such amount of fuel type used is sufficient to allow the refractory particles accompanying it when sprayed in the presence of oxygen to melt at least superficially.
Kot gorivo je mogoče izbrati številne različne materiale pod pogojem, da hitro oksidirajo ob velikem sproščanju toplote ob tvorbi žarovzdržnega oksida. Delci silicija, aluminija in/ali magnezija tvorijo žarovzdržne okside in to prispeva k izdelavi kompaktnih, zelo kvalitetnih mas, ki ne vsebujejo vključkov, nekompatibilnih z dobro toplotno obstojnostjo.Many different materials can be selected as fuel provided they are rapidly oxidized with high heat release upon the formation of refractory oxide. Particles of silicon, aluminum and / or magnesium form refractory oxides, and this contributes to the production of compact, high-quality, non-inclusions incompatible materials with good thermal resistance.
Predloženi izum se nanaša tudi na žarovzdržno maso, ki vsebuje dispergirane delce ogljika in jo izdelamo po zgoraj opisanem postopku, kot tudi na žarovzdržno maso, ki vsebuje dispergirane delce ogljika in ki jo izdelamo z brizganjem zmesi, kot je spredaj opisano v prisotnosti kisika.The present invention also relates to a refractory containing dispersed carbon particles produced by the process described above, as well as to a refractory containing dispersed carbon particles produced by spraying a mixture as described above in the presence of oxygen.
Predloženi izum bomo podrobneje opisali z naslednjimi primeri.The present invention will be described in more detail with the following examples.
PRIMER 1EXAMPLE 1
Žarovzdržno maso nanesemo na konvertersko steno, ki obstoji iz opek iz magnezije-ogljikaj z naslednjo sestavo: MgO 90 %, C 10 %. Na te opeke brizgamo zmes žarovzdržnih delcev, delcev goriva, ki se dajo eksotermno oksidirati, da dobimo žarovzdržen oksid, in delcev, ki vsebujejo ogljik in so manj podvrženi popolni oksidaciji. Stena ima temperaturo 900 °C. Zmes brizgamo s hitrostjo 500 kg/h v plinskem toku, ki vsebuje 70 vol.% kisika. Zmes ima naslednjo sestavo:The heat-resistant mass is applied to a converter wall consisting of magnesium-carbon bricks with the following composition: MgO 90%, C 10%. These bricks are sprayed with a mixture of refractory particles, exothermally oxidized fuel particles to produce refractory oxide, and carbon-containing particles that are less subject to complete oxidation. The wall has a temperature of 900 ° C. The mixture was sprayed at a rate of 500 kg / h in a gas stream containing 70% by volume of oxygen. The mixture has the following composition:
Delci silicija imajo srednjo velikost zrn 10 pm in specifično površino 5000 cm2/g. Delci aluminija imajo srednjo velikost zrn 10 jun in specifično površino 8000 cm2/g. Delci ogljika so delci, ki jih dobimo z mletjem koksa, njihova srednja velikost i - pa je 1,25 mm. Ko to zmes brizgamo na vročo steno, delci silicija in aluminija zgorijo, pri čemer sprostijo dovolj toplote, da povzročijo vsaj površinsko staljenje delcev magnezije. Ti delci MgO imajo srednjo velikost zrn 1 mm. Med brizganjem se delci koksa površinsko spajajo s kisikom, s čimer je omogočeno, da ostanejo neoksidi rana ogljična jedra s srednjo velikostjo zrn 200 pm, ki so okludirana v masi, naneseni na obdelani površini. Izdelana žarovzdržna masa vsebuje približno 3 % ogljika. Zelo dobro se oprime stene, celo če je pred brizganjem na steni prevleka žlindre, njena sestava in kompaktnost pa sta taki, da zdrži erozijo in korozijo ob stiku s staljenim jeklom.Silicon particles have a mean grain size of 10 pm and a specific surface area of 5000 cm 2 / g. The aluminum particles have a mean grain size of 10 June and a specific surface area of 8000 cm 2 / g. Carbon particles are particles obtained by grinding coke and their mean size i is 1.25 mm. When this mixture is sprayed onto the hot wall, the silica and aluminum particles burn, releasing enough heat to cause at least surface melting of the magnesium particles. These MgO particles have a mean grain size of 1 mm. During the spraying, the coke particles are surface bonded to oxygen, allowing the non-oxide wound carbon cores with a medium grain size of 200 µm to be occluded in the mass deposited on the treated surface. The produced refractory mass contains about 3% carbon. It adheres to the wall very well, even if the slag coating is sprayed on the wall and its composition and compactness are such as to withstand erosion and corrosion upon contact with molten steel.
Podobne rezultate smo dosegli tudi z nadomestitvijo delcev koksa z delci ogljika, izdelanimi z mletjem ostankov elektrod.Similar results were obtained by replacing coke particles with carbon particles produced by grinding electrode residues.
PRIMER 2EXAMPLE 2
Ponovili smo postopek, opisan v primeru 1, vendar smo v brizgano zmes dodali nadaljnje delce silicija, ki naj bi ostali v elementarni obliki, da bi izdelali žarovzdržno maso, ki vsebuje kovino. Ti delci imajo srednjo velikost zrn 35 jam. Reaktivnost teh delcev proti kisiku zmanjšamo z oksidiranjem njihove površine, predno jih uporabimo v zmesi. Okoli delcev oblikujemo lupino oksida s tem, da jih obdelamo v fluidizirani blazini vročega kisika. Z brizganjem te zmesi na steno, ki obstoji iz opek iz magnezije_ogljika, izdelamo na njej kompaktno maso, ki je zlasti obstojna proti koroziji v stiku z vročo atmosfero konverterja, staljenim jeklom in njegovimi žlindrami.The procedure described in Example 1 was repeated, but further silica particles were added to the injection mixture to remain in elemental form to produce a refractory metal-containing mass. These particles have a mean grain size of 35 pits. The reactivity of these particles against oxygen is reduced by oxidizing their surface before being used in the mixture. An oxide shell is formed around the particles by treating them in a fluidized bed of hot oxygen. By spraying this mixture on a wall consisting of magnesium_ carbon bricks, a compact mass is produced on it, which is particularly resistant to corrosion in contact with the converter's hot atmosphere, molten steel and its slag.
Pri izvedbeni varianti nadaljnji delci silicija, ki naj ostanejo v izdelani masi, nimajo plaščev za zaščito proti oksidaciji, namesto tega pa imajo minimalni premer 100 pm. Z uporabo zmesi, ki vsebuje take nadaljnje delce, dosežemo rezultate, ki so podobni zgoraj navedenim rezultatom.In the embodiment, the further silicon particles which are to be retained in the fabricated mass do not have oxidation shielding jackets and instead have a minimum diameter of 100 pm. By using a mixture containing such further particles, results are obtained that are similar to the above results.
PRIMER 3EXAMPLE 3
Zmes delcev, ki obstoji iz žarovzdržnega MgO, silicijevega in aluminijevega goriva in ogljika, ki obstoji iz jedra ogljika, na katerega smo nanesli sloj aluminijevega oksida, brizgamo na steno, ki obstoji iz žarovzdržne ga materiala tipa magnezija-ogljik pri temperaturi 900 °C. Hitrost brizganja je 100 kg/h v plinskem toku, ki vsebuje 70 % kisika (vol.). Zmes ima K; naslednjo sestavo:A particle mixture consisting of refractory MgO, silicon and aluminum fuel and carbon consisting of a carbon core to which a layer of aluminum oxide was applied is sprayed onto a wall consisting of a refractory magnesium-carbon material at 900 ° C. The injection rate is 100 kg / h in a gas stream containing 70% oxygen (vol.). The mixture has a K; the following composition:
MgO 75 mas.%MgO 75% by weight
Si 4 mas.%Si 4 wt.%
Al 4 mas.%Al 4 wt.%
C 17 mas.%C 17% by weight
Delci silicija in aluminija imajo srednjo velikost zrn in specifično površino, podobno kot je omenjeno v primeru 1. Delci ogljika imajo srednjo velikost zrn 1 mm, aluminijev oksid pa je prisoten v količini 1 % glede na maso ogljika. Oksid nanesemo na delce ogljika z nanašanjem aluminija na delce pod vakuumom in nato z oksidiranjem kovinskega sloja. Z brizganjem te zmesi na vročo žarovzdržno steno dobimo kompaktno maso, ki se dobro oprime in vsebuje več kot 10 % ogljika.The silicon and aluminum particles have a medium grain size and a specific surface area similar to that mentioned in Example 1. The carbon particles have a mean grain size of 1 mm and the alumina is present in an amount of 1% by weight of carbon. The oxide is applied to the carbon particles by applying aluminum to the particles under vacuum and then oxidizing the metal layer. By spraying this mixture on a hot refractory wall, a compact mass is obtained which holds well and contains more than 10% carbon.
Pri alternativni izvedbi izvedemo zgoraj opisani postopek tako, da nadomestimo delce ogljika^ preslojene z aluminijevim oksidom, z delci ogljika, na katere smo nanesli sloj titanovega oksida. Sloj titanovega oksida nanesemo na delce s pomešanjem delcev s tekočim organskim orto-titanatom, nato razkrojimo titanat pri temperaturi reda velikostiIn the alternative embodiment, the procedure described above is performed by replacing the carbon particles coated with aluminum oxide with the carbon particles to which a layer of titanium oxide was applied. The titanium oxide layer is applied to the particles by mixing the particles with liquid organic ortho-titanate, then decomposing the titanate at a temperature of the order of magnitude
500 °C. Tako dosežemo rezultat, ki je popolnoma podoben zgoraj opisanemu.500 ° C. This results in a result quite similar to the one described above.
PRIMER 4 žarovzdržno maso nanesemo na steno pri temperaturi 900 °C. Stena obstoji iz žarovzdržnega materiala, ki vsebuje ogljik. Ima naslednjo sestavo: Al^O^ 85 %, C 15 %. Zmes žarovzdržnih delcev, delcev goriva in delcev ogljikove spojine brizgamo na površino te stene s hitrostjo 200 kg/h v nosilnem plinu, ki vsebuje 70 % kisika (vol.). Značilnosti zmesi so naslednje:EXAMPLE 4 Heat-resistant mass was applied to the wall at 900 ° C. The wall consists of a heat-resistant carbon-containing material. It has the following composition: Al ^ O ^ 85%, C 15%. A mixture of refractory particles, fuel particles and carbonaceous particles is sprayed onto the surface of this wall at a rate of 200 kg / h in a carrier gas containing 70% oxygen (vol.). The characteristics of the mixture are as follows:
Žarovzdržni delci imajo velikost zrn med 300 pm in 1 mm, delci silicijevega goriva pa imajo karakteristike, ki so podobne karakteristikam, opisanim v primeru 1. Delci ogljikove spojine imajo srednjo velikost zrn pod 50 |im in obstoje iz mletega poliakrilonitrila. Med brizganjem ti delci karbonizirajo in dobljeni ogljik se okludira v žarovzdržni masi, ki se oprijema vroče stene. Na ta način izdelamo dobro kompaktirane žarovzdržne mase, ki so odporne proti eroziji pri stiku s tekočimi kovinami in njihovimi žlindram!.Refractory particles have a grain size between 300 µm and 1 mm, and silica particles have characteristics similar to those described in Example 1. The carbonaceous particles have a mean grain size below 50 µm and are made of ground polyacrylonitrile. During injection, these particles carbonate and the resulting carbon is occluded in a heat-resistant mass adhering to the hot wall. In this way we produce well compacted heat-resistant masses that are resistant to erosion by contact with liquid metals and their slag !.
Pri variantah nadomestimo prah poliakrilonitrila s prahom saharoze, s fenolno smolo, epoksi smolo in polialil kloridom ter dobimo podobne rezultate. V nekaterih primerih je lahko ugodno, da zadržimo karboniziranje teh materialov s prekrivanjem delcev s samougasljivo polimerno prevleko.In the variants, the polyacrylonitrile powder is replaced by sucrose powder, phenolic resin, epoxy resin and polyallyl chloride, and similar results are obtained. In some cases, it may be advantageous to retain the carbonation of these materials by coating the particles with a self-extinguishing polymer coating.
Najboljši način za gospodarsko izkoriščanje izumaThe best way to make economic use of the invention
Žarovzdržno maso nanesemo na konvertersko steno, ki obstoji iz opek iz magnezije-ogljika zsnaslednjo sestavo: MgO 90 %, C 10 %. Na te opeke brizgamo zmes žarovzdržnih delcev, delcev goriva, ki se dajo eksotermno oksidirati, da dobimo 'žarovzdržen oksid, in delcev, ki vsebujejo ogljik in so manj podvrženi popolni oksidaciji. Stena ima temperaturo 900 °C. Zmes brizgamo s hitrostjo 500 kg/h v plinskem toku, ki vsebuje 70 vol.% kisika. Zmes ima naslednjo sestavo:The heat-resistant mass is applied to a converter wall consisting of magnesium-carbon bricks of the following composition: MgO 90%, C 10%. These bricks are sprayed with a mixture of refractory particles, exothermally oxidized fuel particles to produce refractory oxide, and carbon-containing particles that are less subject to complete oxidation. The wall has a temperature of 900 ° C. The mixture is sprayed at a rate of 500 kg / h in a gas stream containing 70% by volume of oxygen. The mixture has the following composition:
Delci silicija imajo srednjo velikost zrn 10 pra in specifično površino 5000 cm2/g. Delci aluminija imajo srednjo velikost zrn 10 pm in specifično površino 8000 cm2/g. Delci ogljika so delci, ki jih dobimo z mletjem koksa, njihova srednja velikost pa je 1,25 mm. Ko to zmes brizgamo na vročo steno, delci silicija in aluminija zgorijo, pri čemer sprostijo dovolj toplote, da povzročijo vsaj površinsko staljenje delcev magnezije. Ti delci MgO imajo srednjo velikost zrn 1 mm. Med brizganjem se delci koksa površinsko spajajo s kisikom, s čimer je omogočeno, da ostanejo neoksidi rana ogljična jedra s srednjo velikostjo zrn 200 pm, ki so okludirana v masi, naneseni na obdelani površini. Izdelana žarovzdržna masa vsebuje približno 3 % ogljika. Zelo dobroThe silica particles have a mean grain size of 10 pra and a specific surface area of 5000 cm 2 / g. The aluminum particles have a mean grain size of 10 pm and a specific surface area of 8000 cm 2 / g. Carbon particles are particles obtained by grinding coke with a mean size of 1.25 mm. When this mixture is sprayed onto the hot wall, the silica and aluminum particles burn, releasing enough heat to cause at least surface melting of the magnesium particles. These MgO particles have a mean grain size of 1 mm. During the spraying, the coke particles are surface bonded to oxygen, allowing the non-oxide wound carbon cores with a medium grain size of 200 µm to be occluded in the mass deposited on the treated surface. The produced refractory mass contains about 3% carbon. Very good
- 25se oprime stene, celo če je pred brizganjem na steni prevleka žlindre, njena sestava in kompaktnost pa sta taki, da ‘Zdrži erozijo in korozijo ob stiku s staljenim jeklom.- 25All adhesion to the wall, even if there is a coating of slag on the wall prior to spraying, and its composition and compactness are such as to 'Withstand erosion and corrosion upon contact with molten steel.
Podobne rezultate smo dosegli tudi z nadomestitvijo delcev koksa z delci ogljika, izdelanimi z mletjem ostankov elektrod.Similar results were obtained by replacing coke particles with carbon particles produced by grinding electrode residues.
Claims (15)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU86431A LU86431A1 (en) | 1986-05-16 | 1986-05-16 | METHOD FOR FORMING A REFRACTORY MASS ON A SURFACE AND MIXING PARTICLES TO FORM SUCH A MASS |
| YU86887A YU45821B (en) | 1986-05-16 | 1987-05-14 | PROCEDURE FOR MANUFACTURE OF COHERENT SURFACE-RESISTANT MASS ON SURFACE AND MIXTURE OF PARTICLES FOR MANUFACTURE OF SUCH MASS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SI8710868A8 true SI8710868A8 (en) | 1996-08-31 |
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ID=26640316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SI8710868A SI8710868A8 (en) | 1986-05-16 | 1987-05-14 | Procedure for making coherent fire resistant material on the surface and mixture of small parts for making such material |
Country Status (2)
| Country | Link |
|---|---|
| HR (1) | HRP921356A2 (en) |
| SI (1) | SI8710868A8 (en) |
-
1987
- 1987-05-14 SI SI8710868A patent/SI8710868A8/en unknown
-
1992
- 1992-11-25 HR HR921356A patent/HRP921356A2/en not_active Application Discontinuation
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| HRP921356A2 (en) | 1995-08-31 |
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