TW201319003A - Components of plant, such as reduction furnace body and/or electrode, in particular for a reduction furnace - Google Patents

Abstract

Component of a plant for the production of silicon, in particular liquid silicon and solar grade silicon, wherein the component is a reduction furnace body and/or an electrode that comprise a composition selected from (i) 80-95 % (w/w) of a silicon carbide product containing 1.5 ppm (w/w) or less boron and 3.0 ppm (w/w) or less phosphorus; (ii) 5-20 % (w/w) of a silicon product containing 1.5 ppm (w/w) or less boron and 3.0 ppm (w/w) or less phosphorus; and (iii) 0.1-5 % (w/w) of a binding agent, such as a resin, e.g. a synthetic resin; and, wherein the sum of this composition is 100 % (w/w) before a curing process, a process for the production as well as the use of the silicon containing material.

Description

設備組件，如還原爐體及/或電極，尤其是還原爐者 Equipment components, such as reduction furnace bodies and/or electrodes, especially reduction furnaces

本揭示特別關於製造太陽能等級矽之領域以及金屬在電弧爐中之處理。尤其是，其關於還原爐之電極，更佳係關於用於進行石英之碳熱還原的還原爐之電極。 The present disclosure is particularly directed to the field of manufacturing solar grade germanium and the processing of metals in electric arc furnaces. In particular, the electrode for the reduction furnace is more preferably an electrode for a reduction furnace for performing carbothermal reduction of quartz.

因此，本發明目的係用於藉由碳熱還原來製造矽之設備組件，其中該組件為還原爐體之內部襯裡或電極，該組件具有選自以下之組成物：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(iii)0.1-5%(w/w)之黏結劑，如樹脂，例如合成樹脂；且，其中此組成物於固化前的總合為100%(w/w)；該含矽材料之製造方法以及用途。 Accordingly, the present invention is directed to an apparatus assembly for the manufacture of crucibles by carbothermal reduction, wherein the assembly is an internal liner or electrode of a reduction furnace body having a composition selected from the group consisting of: (i) 80-95% (w/w) a niobium carbide product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus; (ii) 5-20% (w/w) a bismuth product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus; and (iii) 0.1-5% (w/w) of a binder, such as a resin, For example, a synthetic resin; and wherein the total composition of the composition before curing is 100% (w/w); a method for producing the cerium-containing material and use thereof.

部分因全球暖化的疑慮之故，太陽能電池板的需求持續成長。因此，對於製備用以製造太陽能電池板所需之矽的具有成本效益及環保(即，具有能源效益)方法的需求亦持續成長。有數種製造矽之方式。該等方式當中包括：涉及以酸處理冶金矽，然後與HCl氣相反應及使用氫在矽棒上氣相分解的方法。此種已知為西門子法(Siemens Process)的化學方法消耗大量能源，因此相當昂貴。 Part of the demand for solar panels continues to grow due to concerns about global warming. Therefore, the demand for cost-effective and environmentally friendly (ie, energy-efficient) methods for preparing the enthalpy for manufacturing solar panels continues to grow. There are several ways to make a flaw. Among these methods are those involving the treatment of metallurgical crucibles with an acid, followed by gas phase reaction with HCl and gas phase decomposition on a crucible using hydrogen. Such a chemical process known as the Siemens Process consumes a large amount of energy and is therefore quite expensive.

進行涉及使用熔渣及氣體精製半純液態矽然後凝固之 物理純化方法。將固態產物壓碎，並瀝濾出Fe、Al、Ca及Ti。然後將該產物再熔融且進行定向凝固。此方法係由Elkem Company所使用。 Performing a process involving the purification of semi-pure liquid helium using slag and gas and then solidifying Physical purification method. The solid product is crushed and leached out of Fe, Al, Ca and Ti. The product is then remelted and directional solidification is carried out. This method is used by the Elkem Company.

在第三方法中，使純石英進行碳熱還原以獲得矽液體，該矽液體可藉由下列步驟處理：氣體精製、溫度調整、沉降、過濾、撇渣及定向凝固。使用該方法之挑戰係製造具有充足純度的矽產物。 In the third method, pure quartz is subjected to carbothermal reduction to obtain a hydrazine liquid which can be treated by the following steps: gas refining, temperature adjustment, sedimentation, filtration, slag, and directional solidification. The challenge of using this method is to produce a hydrazine product of sufficient purity.

本發明人已暸解以石英之碳熱還原為基礎然後藉由在液態下精製的方法是用製造太陽能等級矽的有前途之替代方法。但碳熱還原成矽的一般問題為雜質累積及能源消耗。尤其是，由於在電弧爐中還原期間的高處理溫度，金屬雜質會因在高溫下其遷移率提高而從爐之襯裡釋出，因此雜質容易從與該矽接觸的爐部分釋放至液態矽。 The inventors have appreciated that a method based on the carbothermal reduction of quartz and then refined in a liquid state is a promising alternative to the manufacture of solar grade germanium. However, the general problem of carbothermal reduction to bismuth is impurity accumulation and energy consumption. In particular, due to the high processing temperature during reduction in the electric arc furnace, metal impurities are released from the lining of the furnace due to an increase in mobility at a high temperature, so that impurities are easily released from the furnace portion in contact with the crucible to the liquid helium.

相較於最新技術方法，碳熱還原法比上述物理純化方法具有低投資成本、低操作成本及低能源消耗，於此方法中之碳熱還原之後移除的雜質較少，且本發明人已選用以代替使用較高純度之起始材料。因此，本發明人的結論係碳熱還原期間液態矽不受污染是極為重要的。尤其是，本發明人已發現若進行碳熱還原之還原爐的內部襯裡具有特定純度之組分的組成物，則該碳熱還原之產物不受污染。此外，本發明人已發現若用於製造太陽能等級矽之設備組件的關鍵部分或內部襯裡裝配有高純度硼、磷及其他金 屬，則可有效避免受矽以外之其他金屬污染。因此，本發明人已發現在該等高溫、侵蝕性及腐蝕性條件下形成安定組件的可用之特定組成物。 Compared with the latest technical methods, the carbothermal reduction method has lower investment cost, lower operating cost and low energy consumption than the above physical purification method, and the impurities removed by the carbothermal reduction in this method are less, and the inventors have Instead of using a higher purity starting material. Therefore, the inventors have concluded that it is extremely important that liquid helium is not contaminated during carbothermal reduction. In particular, the inventors have found that if the internal lining of the reduction furnace of the carbothermal reduction has a composition of a component of a specific purity, the product of the carbothermic reduction is not contaminated. Furthermore, the inventors have discovered that the key parts or internal linings of equipment components used in the manufacture of solar grade crucibles are equipped with high purity boron, phosphorus and other gold. Genus, it can effectively avoid contamination of other metals besides cockroaches. Accordingly, the inventors have discovered that specific compositions useful for forming a stability component under such high temperature, aggressive, and corrosive conditions have been discovered.

此外，本發明人已發現若電極及/或電極的至少一些組件(諸如電極主體、電源連接、螺紋接管、閉鎖銷、安裝座、夾片，彼等係在碳熱還原期間與反應物或可動電極接觸)具有特定純度之組分的組成物，則該碳熱還原產物不受污染。因此，在碳熱還原之後進行數個較不複雜且具有能源效益之液態精製步驟之後，可獲得具有太陽能電池製造商需要的特徵之矽產物。 Furthermore, the inventors have discovered that if at least some components of the electrodes and/or electrodes (such as electrode bodies, power connections, nipples, latching pins, mounts, clips, etc., are reactive or reactive during carbothermal reduction) The electrode is contacted with a composition having a component of a specific purity, and the carbothermal reduction product is not contaminated. Thus, after several less complex and energy efficient liquid refining steps after carbothermal reduction, a ruthenium product having the characteristics required by the solar cell manufacturer can be obtained.

又，特別困難因此相當昂貴的是在碳熱還原步驟之後的移除硼及磷精製步驟。因此，特別重要的是該碳熱還原產物不受此等元素污染。 Again, it is particularly difficult and therefore quite expensive to remove the boron and phosphorus refining steps after the carbothermal reduction step. Therefore, it is particularly important that the carbothermal reduction product is not contaminated by such elements.

因此，本發明目的係對用於製造太陽能等級矽之設備裝配其他組件，尤其是諸如硼、磷及尤其是金屬雜質(較佳係除矽以外之所有金屬)的污染程度非常低之電弧爐的組件。此等部分除了必須耐熱之外，其在高溫下亦具有特定傳導率。另一目的係提供在使用期間腐蝕程度較低或不降低產率的組件。第三目的係提出用於製造此等該等組件的方法。此外，該等組件應具有較長使用壽命。 Accordingly, the present invention is directed to the assembly of other components for equipment for the manufacture of solar grade crucibles, especially for electric arc furnaces having very low levels of contamination such as boron, phosphorus and especially metallic impurities, preferably all metals other than helium. Component. In addition to being heat resistant, these parts also have a specific conductivity at high temperatures. Another object is to provide an assembly that has a low or no reduction in yield during use. A third object is to propose a method for manufacturing such components. In addition, these components should have a long service life.

因此，本發明之具體實例為用於藉由碳熱還原來製造矽(尤其是液態矽及太陽能等級矽)之設備組件，其中該組 件包含：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼，及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(iii)0.1-5%(w/w)之黏結劑反應產物及/或黏結劑，如樹脂，例如合成樹脂；且其中此組成物的總合為100%(w/w)。 Accordingly, a specific example of the present invention is an apparatus component for producing ruthenium (especially liquid ruthenium and solar grade ruthenium) by carbothermal reduction, wherein the group The article comprises: (i) 80-95% (w/w) of a niobium carbide product containing 1.5 ppm (w/w) or less of boron, and 3.0 ppm (w/w) or less of phosphorus; 5-20% (w/w) of a cerium product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus; and (iii) 0.1-5% ( W/w) a binder reaction product and/or a binder such as a resin such as a synthetic resin; and wherein the total composition of the composition is 100% (w/w).

用於藉由碳熱還原來製造液態矽之較佳設備的組件係選自還原爐體之內部襯裡；SiC爐之內部襯裡；加熱或乾燥烘箱之內部襯裡；製粒、製錠、壓塊設備之內部襯裡；擠出器、電極組件、電極、放液通道、供給通道、連接部分、放液設備之組件、澆斗、坩堝之內部襯裡；保溫爐之內部襯裡；定向凝固爐之內部襯裡；與石英、碳化矽、矽產物或包含石英、碳化矽、矽產物中任一者之調配物接觸的裝置之襯裡；供給通道之內部襯裡及供給管之內部襯裡。 The component for the preferred apparatus for producing liquid helium by carbothermal reduction is selected from the interior lining of the reduction furnace body; the internal lining of the SiC furnace; the internal lining of the heating or drying oven; the granulation, ingot making, briquetting equipment Internal lining; extruder, electrode assembly, electrode, draining channel, supply channel, connecting portion, assembly of liquid discharging device, internal lining of bucket, crucible; internal lining of holding furnace; internal lining of directional solidification furnace; Lining of a device in contact with quartz, tantalum carbide, niobium product or a formulation comprising any of quartz, tantalum carbide, niobium products; internal lining of the supply channel and internal lining of the supply tube.

特別獨立的是，(i)及/或(ii)含有1.0 ppm(w/w)或更少之硼，尤其是等於或少於0.7 ppm(w/w)，較佳為等於或少於0.2 ppm(w/w)至0.001 ppt(w/w)之硼，及3.0 ppm(w/w)或更少之磷，尤其是等於或少於0.5 ppm(w/w)，較佳為等於或少於0.1 ppm(w/w)至0.001 ppt(w/w)之磷。 Particularly independent, (i) and / or (ii) contain 1.0 ppm (w/w) or less of boron, especially equal to or less than 0.7 ppm (w/w), preferably equal to or less than 0.2. Pour ppm (w/w) to 0.001 ppt (w/w) of boron, and 3.0 ppm (w/w) or less of phosphorus, especially equal to or less than 0.5 ppm (w/w), preferably equal to or Less than 0.1 ppm (w/w) to 0.001 ppt (w/w) of phosphorus.

尤其是，組件包含的該碳化矽產物或矽產物中之所有其他金屬(排除矽)的總和分別少於100 ppm(w/w)，其中 尤其是該等其他金屬係選自Ag、Al、As、Au、Ba、Be、Bi、Ca、Cd、Ce、Co、Cr、Cs、Cu、Dy、Er、Eu、Fe、Ga、Gd、Ge、Hf、Hg、Ho、In、Ir、K、La、Li、Lu、Mg、Mn、Mo、Na、Nb、No、Os、Pb、Pd、Pr、Pt、Rb、Re、Rh、Ru、Sb、Sc、Se、Sm、Sn、Ta、Tb、Te、Th、Ti、Tl、Tm、U、W、Y、Yb、Zn、Zr，或其中該碳化矽產物及該矽產物中之該等其他金屬的總和少於100 ppm(w/w)，尤其是少於80 ppm(w/w)，較佳為少於50 ppm(w/w)，且尤其是少於10 ppm(w/w)的鐵。 In particular, the sum of the other niobium carbide products or all other metals in the niobium product (excluding niobium) contained in the assembly is less than 100 ppm (w/w), respectively. In particular, the other metals are selected from the group consisting of Ag, Al, As, Au, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge. , Hf, Hg, Ho, In, Ir, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, No, Os, Pb, Pd, Pr, Pt, Rb, Re, Rh, Ru, Sb , Sc, Se, Sm, Sn, Ta, Tb, Te, Th, Ti, Tl, Tm, U, W, Y, Yb, Zn, Zr, or the other of the niobium carbide products and the niobium product The sum of the metals is less than 100 ppm (w/w), especially less than 80 ppm (w/w), preferably less than 50 ppm (w/w), and especially less than 10 ppm (w/w) Iron.

使用高純度矽作為本發明之金屬雜質總和少於5 ppm(w/w)的組成物，該糊中之金屬的整體含量可低於80 ppm (w/w)，或更佳為少於50 ppm(w/w)至0.0001 ppt(w/w)。 Using high purity ruthenium as a composition having less than 5 ppm (w/w) of metal impurities in the present invention, the overall content of the metal in the paste may be less than 80 ppm (w/w), or more preferably less than 50 ppm (w/w) to 0.0001 ppt (w/w).

更佳情況係，該組件當中該碳化矽產物及該矽產物中選自下列的該等其他金屬係等於或少於：a.鋁(Al)30 ppm(w/w)或為25至0.0001 ppt(w/w)，尤其是22 ppm(w/w)至0.0001 ppt(w/w)，及b.硼(B)1.0 ppm(w/w)至0.0001 ppt(w/w)，尤其是0.5 ppm(w/w)至0.0001 ppt(w/w)，較佳為0.4 ppm(w/w)至0.0001 ppt(w/w)，或特佳為0.35 ppm(w/w)至10 ppb(w/w)；及c.鈣(Ca)20 ppm(w/w)，尤其是15至0.0001 ppt(w/w)，較佳為10 ppm(w/w)至0.0001 ppt(w/w)；及隨意的d.鎵(Ga)1 ppm，尤其是0.5 ppm至0.0001 ppt(w/w)，較佳為0.1 ppm(w/w)至0.0001 ppt(w/w)，尤佳為1 ppb(w/w)至0.0001 ppt(w/w)，e.鎳(Ni)10 ppm(w/w)，尤其是5 ppm(w/w)至0.0001 ppt(w/w)，較佳為3.5 ppm及0.0001 ppt(w/w)；f.磷(P)3 ppm(w/w)至0.0001 ppt(w/w)，尤其是2 ppm(w/w)至0.0001 ppt(w/w)，較佳為1 ppm(w/w)至0.0001 ppt(w/w)，及g.鈦(Ti)2 ppm(w/w)，尤其是1.7 ppm(w/w)至0.0001 ppt，較佳為1.5至0.0001 ppt(w/w)；及h.鋅(Zn)30 ppm(w/w)，尤其是25 ppm(w/w)至0.0001 ppt(w/w)，較佳為10 ppm至0.0001 ppt(w/w)。 More preferably, the niobium carbide product and the other metal of the niobium product selected from the group are equal to or less than: a. aluminum (Al) 30 ppm (w/w) or 25 to 0.0001 ppt. (w/w), especially 22 ppm (w/w) to 0.0001 ppt (w/w), and b. boron (B) 1.0 ppm (w/w) to 0.0001 ppt (w/w), especially 0.5 Ppm (w/w) to 0.0001 ppt (w/w), preferably 0.4 ppm (w/w) to 0.0001 ppt (w/w), or particularly preferably 0.35 ppm (w/w) to 10 ppb (w) /w); and c. calcium (Ca) 20 ppm (w / w), especially 15 to 0.0001 ppt (w / w), preferably 10 ppm (w / w) to 0.0001 ppt (w / w); And optionally d. gallium (Ga) 1 ppm, especially 0.5 ppm to 0.0001 ppt (w/w), preferably 0.1 ppm (w/w) to 0.0001 ppt (w/w), especially preferably 1 ppb ( w/w) to 0.0001 ppt (w/w), e. nickel (Ni) 10 ppm (w/w), especially 5 ppm (w/w) to 0.0001 ppt (w/w), preferably 3.5 ppm And 0.0001 ppt(w/w); f. phosphorus (P) 3 ppm (w/w) to 0.0001 ppt (w/w), especially 2 ppm (w/w) to 0.0001 ppt (w/w), Preferably, it is from 1 ppm (w/w) to 0.0001 ppt (w/w), and g. titanium (Ti) 2 ppm (w/w), especially from 1.7 ppm (w/w) to 0.0001 ppt, preferably 1.5. To 0.0001 ppt(w/w); and h. zinc (Zn) 30 ppm (w/w), especially 25 ppm (w/w) to 0.0001 Ppt (w/w) is preferably from 10 ppm to 0.0001 ppt (w/w).

根據一具體實例，該組件為未淬火體且包含選自以下之組成物：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；其中該矽產物為矽，及(iii)0.1-5%(w/w)之黏結劑，諸如樹脂、碳水化合物，例如合成樹脂、酚-甲醛樹脂及/或醣；且其中此組成物的總合為100%(w/w)。通常，該矽之純度為至少等於或大於99.9999%(w/w)，較佳為99.99999%(w/w)，更佳為等於或大於99.999999%(w/w)。 According to a specific example, the assembly is an unquenched body and comprises a composition selected from the group consisting of: (i) 80-95% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 ppm ( w/w) or less phosphorus niobium carbide product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or more a ruthenium product of less phosphorus; wherein the ruthenium product is ruthenium, and (iii) 0.1 to 5% (w/w) of a binder such as a resin, a carbohydrate such as a synthetic resin, a phenol-formaldehyde resin and/or a sugar; And wherein the total composition of this composition is 100% (w/w). Typically, the purity of the crucible is at least equal to or greater than 99.9999% (w/w), preferably 99.99999% (w/w), more preferably equal to or greater than 99.999999% (w/w).

尤其是，該組件(尤其是粗製且經加熱組件/體)包含選自以下之組成物：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；其中該矽產物包含氮化矽及隨意的矽，及(iii)0至5(w/w)之黏結劑反應產物，諸如樹脂、碳水化合物，例如合成樹脂及/或醣，且其中此組成物的總合為100%(w/w)。 In particular, the component (especially the crude and heated component/body) comprises a composition selected from the group consisting of: (i) 80-95% (w/w) containing 1.5 ppm (w/w) or less of boron And 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/ w) or less of a bismuth product of phosphorus; wherein the bismuth product comprises cerium nitride and optionally cerium, and (iii) 0 to 5 (w/w) of a binder reaction product such as a resin, a carbohydrate, such as a synthesis Resin and/or sugar, and wherein the total composition of this composition is 100% (w/w).

根據一具體實例，此等部分必須耐熱之外，且在高溫下具有特定傳導率。測得導電率為11 S/cm(T>1480℃)，2A(見表3之經回火及/或加熱SiC組成物在特定樣本溫度下的導電率(S/cm)(例如，證實2A))。導熱率低於12 W/mK(T>900℃)，2C 2E(見表4，導熱率(W/mK))。表5之樣本為2A、2C、2D、2E及2F。 According to a specific example, these parts must be heat resistant and have a specific conductivity at high temperatures. The measured conductivity was 11 S/cm (T>1480 °C), 2A (see Table 3 for tempering and/or heating of the SiC composition at a specific sample temperature (S/cm) (for example, confirming 2A) )). The thermal conductivity is lower than 12 W/mK (T>900 °C), 2C 2E (see Table 4, thermal conductivity (W/mK)). The samples in Table 5 are 2A, 2C, 2D, 2E and 2F.

根據本發明第二實施樣態，一具體實例為一種用於藉由碳熱還原製造液態矽之還原爐體，該爐體包含內部襯裡，其特徵在於該內部襯裡包含：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(ii)0.1-5%(w/w)之黏結劑反應產物及/或黏結劑，如樹脂，例如合成樹脂；尤其是該黏結劑為選自合成酚-甲醛樹脂之樹脂；且，尤其是其中此組成物的總和為100%(w/w)。還原爐體尤其是用於藉由碳熱還原來製造矽、液態矽及/或太陽能等級矽的設備組件。 According to a second embodiment of the present invention, a specific example is a reduction furnace body for producing liquid helium by carbothermal reduction, the furnace body comprising an inner liner, characterized in that the inner liner comprises: (i) 80-95 %(w/w) of niobium carbide containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus; (ii) 5-20% (w/w) a ruthenium product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus; and (ii) 0.1-5% (w/w) of a binder reaction product and / or a binder such as a resin such as a synthetic resin; in particular, the binder is a resin selected from the group consisting of synthetic phenol-formaldehyde resins; and, in particular, wherein the sum of the compositions is 100% (w/w). The reduction furnace body is especially used for the manufacture of equipment components for helium, liquid helium and/or solar grade helium by carbothermal reduction.

又，提出一種用於藉由碳熱還原製造含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物之方法，其包括下列步驟：將含有0.50 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷的石英產物及含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷之碳化矽產物添加至具有內部襯裡之還原爐；及b)加熱該混合物以形成該矽產物的熔體，其中該襯裡包含：80-95%(w/w)之具有與步驟a)中所添加之碳化矽產物至少相同純度的碳化矽產物；5-20%(w/w)之至少具有由該方法所製造之矽產物的純度之矽產物；及0.1-5%(w/w)之黏結劑或黏結劑反應產物，如樹脂。尤其是，所揭示之組成物的總和為 100%(w/w)。 Further, a method for producing a ruthenium product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus by carbothermal reduction is proposed, which comprises the steps of: Quartz product containing 0.50 ppm (w/w) or less of boron and 1.0 ppm (w/w) or less of phosphorus and containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w Or less phosphorus in the reduction furnace; and b) heating the mixture to form a melt of the tantalum product, wherein the liner comprises: 80-95% (w/w) a niobium carbide product having at least the same purity as the niobium carbide product added in step a); 5-20% (w/w) of a niobium product having at least the purity of the niobium product produced by the method; and 0.1-5% (w/w) a binder or binder reaction product, such as a resin. In particular, the sum of the disclosed compositions is 100% (w/w).

此外，該設備組件(尤其是該內部襯裡)必須承受碳熱還原之高溫，且本發明人已選擇該設備組件的組件，尤其是該內部襯裡或電極之組件，因此選擇彼等之性質。如此，80-95%(w/w)，較佳為85-95%(w/w)，更佳為87-93%(w/w)之該組件(尤其是電極或內部襯裡)係由碳化物產物所構成。該碳化物產物含有1.5 ppm(w/w)或更少，較佳為1.0 ppm(w/w)或更少，更佳為0.5 ppm(w/w)或更少，最佳為0.2 ppm(w/w)或更少之B，較佳係低於0.00001 ppm(w/w)。此外，該碳化物產物含有3.0 ppm(w/w)或更少，較佳為2.0 ppm(w/w)或更少，更佳為1.0 ppm(w/w)或更少，最佳為0.5 ppm(w/w)或更少之P，較佳係低於0.00001 ppm(w/w)。此外，5-20%(w/w)，較佳為5-15%(w/w)，更佳為7-13%(w/w)之該組件(尤其是內部襯裡或電極)係由矽產物所構成。該矽產物含有1.5 ppm(w/w)或更少，較佳為1.0 ppm(w/w)或更少，更佳為0.7 ppm(w/w)或更少，最佳為0.5 ppm(w/w)或更少之B。此外，該矽產物含有3.0 ppm(w/w)或更少，較佳為2.0 ppm(w/w)或更少，更佳為1.0 ppm(w/w)或更少，最佳為0.5 ppm(w/w)或更少之P。 Furthermore, the equipment components (especially the inner lining) must withstand the high temperatures of carbothermal reduction, and the inventors have chosen the components of the equipment components, especially the components of the inner lining or electrodes, and therefore select their properties. Thus, 80-95% (w/w), preferably 85-95% (w/w), more preferably 87-93% (w/w) of the component (especially the electrode or the inner lining) is Made up of carbide products. The carbide product contains 1.5 ppm (w/w) or less, preferably 1.0 ppm (w/w) or less, more preferably 0.5 ppm (w/w) or less, and most preferably 0.2 ppm ( w/w) or less B, preferably less than 0.00001 ppm (w/w). Further, the carbide product contains 3.0 ppm (w/w) or less, preferably 2.0 ppm (w/w) or less, more preferably 1.0 ppm (w/w) or less, most preferably 0.5. P of ppm (w/w) or less is preferably less than 0.00001 ppm (w/w). Further, 5-20% (w/w), preferably 5-15% (w/w), more preferably 7-13% (w/w) of the component (especially internal lining or electrode) is The product is composed of hydrazine products. The niobium product contains 1.5 ppm (w/w) or less, preferably 1.0 ppm (w/w) or less, more preferably 0.7 ppm (w/w) or less, and most preferably 0.5 ppm (w). /w) or less B. Further, the hydrazine product contains 3.0 ppm (w/w) or less, preferably 2.0 ppm (w/w) or less, more preferably 1.0 ppm (w/w) or less, and most preferably 0.5 ppm. (w/w) or less P.

根據一具體實例，碳化矽產物含有300 ppm(w/w)，尤其是少於100 ppm(w/w)之Al或更少。根據一替代性或互補性具體實例，矽產物含有100 ppm(w/w)之Al或更少，諸如80 ppm(w/w)之Al或更少，較佳為少於70 ppm (w/w)，少於50 ppm(w/w)。 According to a specific example, the niobium carbide product contains 300 ppm (w/w), especially less than 100 ppm (w/w) Al or less. According to an alternative or complementary embodiment, the niobium product contains 100 ppm (w/w) Al or less, such as 80 ppm (w/w) Al or less, preferably less than 70 ppm. (w/w), less than 50 ppm (w/w).

作為本揭示之第一實施樣態，因此提出用於藉由碳熱還原製造液態矽之還原爐體，該爐體包含內部襯裡，其特徵在於該內部襯裡包含80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼，及3.0 ppm(w/w)或更少之磷的碳化矽產物；5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及0.1-5%(w/w)之黏結劑反應產物及/或黏結劑，如樹脂，或黏結劑反應產物，例如合成酚-甲醛樹脂。 As a first embodiment of the present disclosure, a reduction furnace body for producing liquid helium by carbothermal reduction is proposed, the furnace body comprising an inner liner, characterized in that the inner liner comprises 80-95% (w/w) a niobium carbide product containing 1.5 ppm (w/w) or less of boron, and 3.0 ppm (w/w) or less of phosphorus; 5-20% (w/w) of 1.5 ppm (w/w) ) or less boron and 3.0 ppm (w/w) or less of phosphorus bismuth product; and 0.1-5% (w/w) of binder reaction product and / or binder, such as resin, or binder The reaction product, for example, a synthetic phenol-formaldehyde resin.

此外，其中該還原爐體包含之碳化矽產物或該矽產物各含有少於300 ppm(w/w)，少於100 ppm(w/w)，尤其是少於80 ppm(w/w)之Al或更少，尤其是少於50 ppm(w/w)，較佳為少於30 ppm(w/w)。揭示一種還原爐體，其中該碳化矽產物及該矽產物中所有金屬的總和分別少於100 ppm。(排除矽) Further, wherein the reduction furnace body comprises a niobium carbide product or the niobium product each contains less than 300 ppm (w/w), less than 100 ppm (w/w), especially less than 80 ppm (w/w) Al or less, especially less than 50 ppm (w/w), preferably less than 30 ppm (w/w). A reduction furnace body is disclosed in which the sum of the niobium carbide product and all of the metals in the niobium product are less than 100 ppm, respectively. (excluding 矽)

此外，該還原爐體包含由與該內部襯裡材料不同之材料所構成的第二襯裡，該第二襯裡係配置成與該內部襯裡之外表面接觸。該第二襯裡之材料為矽石或矽石搗製糊。尤其是，將一層石墨或碳搗製糊配置在該爐體底部之內部襯裡及第二襯裡之間。此外，該還原爐體包含配置在該第二襯裡外部的外殼。在較佳具體實例中，將絕緣層配置在該外殼及第二襯裡之間。 Additionally, the reduction furnace body includes a second liner comprised of a different material than the inner liner material, the second liner being configured to contact the outer surface of the inner liner. The material of the second lining is made of vermiculite or vermiculite. In particular, a layer of graphite or carbon crucible paste is disposed between the inner lining of the bottom of the furnace body and the second lining. Further, the reduction furnace body includes an outer casing disposed outside the second liner. In a preferred embodiment, an insulating layer is disposed between the outer casing and the second liner.

根據本發明一具體實例，揭示一還原爐體，其中至少一個電極(較佳係由石墨構成)從該爐體延伸入該爐體底 部。較佳者為電極，較佳係由石墨所構成，其從該爐體上方延伸入該爐體內部。 According to an embodiment of the invention, a reduction furnace body is disclosed, wherein at least one electrode (preferably made of graphite) extends from the furnace body into the furnace bottom unit. Preferably, the electrode is preferably made of graphite which extends from above the furnace body into the interior of the furnace body.

本發明又一具體實例為在爐體底部提供介於爐體內部與外部之間的可關閉之通道以供液態矽放液，且其中該通道的內壁係由該內部襯裡所構成。 Yet another embodiment of the present invention provides a closable passage between the interior and exterior of the furnace body for liquid drainage at the bottom of the furnace body, and wherein the inner wall of the passage is formed by the inner liner.

該還原爐體可特別具有一或多個環繞該爐體內部之電線圈以使得可在該爐體內部產生磁場的配置。及其中該還原爐體被分成上、下部分，其中該上部分係以可旋轉的方式附接於該下部分。 The reduction furnace body may in particular have one or more electrical coils surrounding the interior of the furnace body such that a magnetic field can be created inside the furnace body. And wherein the reduction furnace body is divided into upper and lower portions, wherein the upper portion is rotatably attached to the lower portion.

根據其他具體實例，該碳化矽產物中之所有金屬雜質的總和少於300 ppm(w/w)，尤其是少於100 ppm(w/w)。根據一替代性或互補性具體實例，該矽產物中之所有金屬雜質的總和少於100 ppm(w/w)，諸如少於80 ppm(w/w)，較佳為少於50 ppm(w/w)，更佳為少於10 ppm(w/w)。 According to other embodiments, the sum of all metal impurities in the niobium carbide product is less than 300 ppm (w/w), especially less than 100 ppm (w/w). According to an alternative or complementary embodiment, the sum of all metal impurities in the niobium product is less than 100 ppm (w/w), such as less than 80 ppm (w/w), preferably less than 50 ppm (w) /w), more preferably less than 10 ppm (w/w).

黏結劑能將內部襯裡的組件結合在一起。此外，該內部襯裡組成物應在高溫(諸如高於2000℃之溫度)下安定。樹脂係特別適於此等目的的黏結劑。該樹脂較佳為合成樹脂，諸如通常可具有比天然樹脂更高純度的樹脂，且該樹脂不應包含可相當程度地污染該矽產物的元素。該樹脂可為例如合成酚-甲醛樹脂。具有令人滿意結果的合成樹脂的一特定實例為酚醛清漆(Novolack)。適用樹脂的其他實例為酚醛樹脂(Resol)及Peracit。 The binder bonds the components of the inner lining together. In addition, the internal lining composition should be stabilized at elevated temperatures, such as temperatures above 2000 °C. Resins are particularly suitable binders for these purposes. The resin is preferably a synthetic resin such as a resin which generally has a higher purity than a natural resin, and the resin should not contain an element which can contaminate the niobium product to a considerable extent. The resin may be, for example, a synthetic phenol-formaldehyde resin. A specific example of a synthetic resin having satisfactory results is a novolack. Other examples of suitable resins are phenolic resins (Resol) and Peracit.

然而，本發明人暸解亦可使用其他樹脂。根據一具體 實例，該內部襯裡材料的熱傳導率在1500℃為至少15 W/m°K。該內部襯裡接觸該還原爐中的材料(反應物及產物)。然而，該還原爐體通常包含其他部分以提供適當機械、熱、化學及/或熱傳性質。 However, the inventors know that other resins can also be used. According to a specific By way of example, the internal lining material has a thermal conductivity of at least 15 W/m °K at 1500 °C. The inner liner contacts the materials (reactants and products) in the reduction furnace. However, the reduction furnace body typically contains other parts to provide suitable mechanical, thermal, chemical and/or heat transfer properties.

因此，該還原爐體可包含經配置以與該內部襯裡之外表面接觸的第二襯裡。如此，在此種具體實例中，該第二襯裡的內表面係與該內部襯裡的外表面接觸。該內部襯裡及第二襯裡可被視為不同保護層。該第二襯裡通常由與該內部襯裡材料不同的耐熱性材料所構成。此種材料之實例為矽石搗製糊或矽石，其可具有與添加作為該碳熱還原中之起始材料的石英相同純度。 Accordingly, the reduction furnace body can include a second liner configured to contact the outer surface of the inner liner. Thus, in such a specific example, the inner surface of the second liner is in contact with the outer surface of the inner liner. The inner liner and the second liner can be considered as different protective layers. The second liner is typically constructed of a heat resistant material that is different from the inner liner material. An example of such a material is a vermiculite paste or vermiculite which may have the same purity as the addition of quartz as the starting material in the carbothermal reduction.

根據本發明一具體實例，揭示配備有具有本發明組成物之內部襯裡且尤其是具有用於加熱之構件(諸如感應加熱構件)的澆斗配置，較佳係具有使氣體鼓泡通過底部的構件。尤其是具有用於氯精製之配置，於氯精製期間，將氯氣隨意地連同惰性氣體(諸如氬)鼓泡通過該澆斗中之液態矽，尤其是將該氣體鼓泡通過該澆斗底部，以與雜質(諸如鋁或鈣)反應以形成氯化物鹽，例如AlCl₃及CaCl₂。當鋁氯化物隨後與空氣接觸時，形成對應之氧化物。用於氯精製之配置較佳包含用於加熱該液態矽之構件，諸如感應加熱。此係確使於此程序期間該矽維持液態。因此，本發明另一具體實例為設備組件，尤其是澆斗及/或坩堝，其中該澆斗及/或坩堝包含內部襯裡，其特徵在於該內部襯裡包含：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之 硼，及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(iii)0.1-5%(w/w)之黏結劑反應產物及/或黏結劑，如樹脂，例如合成樹脂；且其中此組成物的總和為100%(w/w)，尤其是該澆斗另外包含加熱構件之配置，較佳之加熱構件為感應加熱構件。該精製亦可在澆斗中完成。該澆斗可藉由加熱元素或藉由使用導應來預熱。 According to an embodiment of the invention, a bucket arrangement equipped with an internal lining having the composition of the invention and in particular having a member for heating, such as an induction heating member, is disclosed, preferably having a member for bubbling gas through the bottom . In particular, having a configuration for chlorine refining, during chlorine refining, the chlorine gas is optionally bubbled through an inert gas such as argon through the liquid helium in the pour, in particular by bubbling the gas through the bottom of the pour, Reacting with impurities such as aluminum or calcium to form chloride salts such as AlCl ₃ and CaCl ₂ . When the aluminum chloride is subsequently contacted with air, a corresponding oxide is formed. The configuration for chlorine refining preferably comprises means for heating the liquid helium, such as induction heating. This is to ensure that the crucible remains liquid during this procedure. Thus, another embodiment of the invention is an apparatus component, particularly a bucket and/or crucible, wherein the bucket and/or crucible comprises an inner liner, characterized in that the inner liner comprises: (i) 80-95% (w) /w) a niobium carbide product containing 1.5 ppm (w/w) or less of boron, and 3.0 ppm (w/w) or less of phosphorus; (ii) 5-20% (w/w) of 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus product; and (iii) 0.1-5% (w/w) of binder reaction product and/or A binder, such as a resin, such as a synthetic resin; and wherein the sum of the compositions is 100% (w/w), in particular, the bucket additionally includes a configuration of a heating member, preferably the heating member is an induction heating member. This refining can also be done in a bucket. The bucket can be preheated by heating the elements or by using a guide.

因此，亦提出一種電極或該電極之至少一組件，其包含具有選自以下之組成物的含矽材料：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及尤其是少於1 ppm(w/w)之所有其他金屬(排除矽)，及(iii)0至5%(w/w)之黏結劑反應產物或黏結劑，尤其是0.1至5.0%(w/w)，諸如樹脂，例如合成樹脂；且其中此組成物的總和為100%(w/w)，尤其是電極或該電極之組件中，較佳係在加熱程序之後。 Accordingly, there is also provided an electrode or at least one component of the electrode comprising a cerium-containing material having a composition selected from the group consisting of: (i) 80-95% (w/w) containing 1.5 ppm (w/w) or Less boron and 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 a plutonium product of ppm (w/w) or less; and especially all other metals (excluding antimony) of less than 1 ppm (w/w), and (iii) 0 to 5% (w/w) a binder reaction product or a binder, especially 0.1 to 5.0% (w/w), such as a resin, such as a synthetic resin; and wherein the sum of the compositions is 100% (w/w), especially an electrode or the electrode Preferably, the assembly is after the heating process.

尤其是在未淬火電極中(例如在固化程序及/或回火程序之前)，該黏合劑的含量較佳為(0.1-5%)(w/w)。Ppm(w/w)具有與ppmw(以重量計之百萬份之份)相同意義。本發明電極之最特殊的特徵係提高在電弧中之液態矽的產率。 Particularly in the unquenched electrode (for example, prior to the curing process and/or the tempering process), the binder is preferably present in an amount of (0.1 to 5%) (w/w). Ppm(w/w) has the same meaning as ppmw (parts by weight). The most particular feature of the electrodes of the present invention is to increase the yield of liquid helium in the arc.

因此，本發明主旨為一種用於藉由碳熱還原製造液態矽之設備組件，尤其是還原爐體、電極、未淬火電極、該未淬火電極之至少一個組件、爐電極(尤其是還原爐之爐電極，較佳為用於製造液態矽之還原爐的爐電極，更佳為用於藉由碳熱還原製造液態矽之還原爐的爐電極)，及/或爐底電極(較佳係該爐底電極可為該反應爐體的至少一部分)之內部襯裡。在較佳具體實例中，該電極為底部電極，較佳為在電弧爐中，更佳為在用於矽製造方法之碳熱還原程序的電弧爐中之底部電極。因此，電極可用作陽極或陰極。 Accordingly, the present invention is directed to an apparatus assembly for producing liquid helium by carbothermal reduction, particularly a reduction furnace body, an electrode, an unquenched electrode, at least one component of the unquenched electrode, a furnace electrode (especially a reduction furnace) The furnace electrode is preferably a furnace electrode for a reduction furnace for producing liquid helium, more preferably a furnace electrode for a reduction furnace for producing liquid helium by carbothermal reduction, and/or a furnace bottom electrode (preferably The bottom electrode can be an internal lining of at least a portion of the reaction furnace body. In a preferred embodiment, the electrode is a bottom electrode, preferably in an electric arc furnace, more preferably a bottom electrode in an electric arc furnace for the carbothermal reduction process of the crucible manufacturing process. Therefore, the electrode can be used as an anode or a cathode.

在本發明之具體實例中，該電極或該電極之部分包括含矽材料，且係選自： In a specific embodiment of the invention, the electrode or a portion of the electrode comprises a cerium-containing material and is selected from the group consisting of:

(i)該電極之大型組件，其係選自電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座及電源連接，或 (i) a large component of the electrode selected from the group consisting of an electrode strand, an electrode body, a nipple, a latching pin, a clip, a heat exchanger, a mount, and a power connection, or

(ii)用於形成該電極之大型組件的至少一部分之其他電極材料的基質，該大型組件係選自電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座及電源連接，或 (ii) a substrate for forming other electrode materials of at least a portion of the large component of the electrode, the large component being selected from the group consisting of electrode strands, electrode bodies, nipples, latching pins, clips, heat exchangers, mounts, and power supplies Connected, or

(iii)用於形成該電極之大型組件的其他電極材料的塗層或塗層之一部分，該大型組件係選自電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座、電源連接，及該等組件的一部分。 (iii) a portion of a coating or coating of other electrode materials used to form the large component of the electrode, the large component being selected from the group consisting of electrode strands, electrode bodies, nipples, latching pins, clips, heat exchangers, mounting Seat, power connection, and part of these components.

(iv)接觸襯裡、密封件、黏著劑及/或結合劑或作為 其一部分，彼等尤其是位於選自以下者之該電極的組件上：電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座及電源連接，或 (iv) contact lining, seals, adhesives and/or bonding agents or as a part thereof, especially on a component of the electrode selected from the group consisting of an electrode strand, an electrode body, a nipple, a latching pin, a clip, a heat exchanger, a mount and a power connection, or

(v)其他電極材料之基質中之該電極的其他組件，該等電極材料尤其是選自石墨及碳化矽，其形成選自以下者之該電極的至少一個組件：電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座及電源連接。此外，在一個電極或電極構造中可結合(i)、(ii)、(iii)、(iv)及/或(v)方面。尤其是(i)及(iii)、(i)及(ii)，隨意地各與(iv)結合。 (v) other components of the electrode in a matrix of other electrode materials, in particular selected from the group consisting of graphite and tantalum carbide, which form at least one component of the electrode selected from the group consisting of electrode strands, electrode bodies, threads Take-up, latching pins, clips, heat exchangers, mounts, and power connections. Furthermore, aspects (i), (ii), (iii), (iv), and/or (v) may be combined in one electrode or electrode configuration. In particular, (i) and (iii), (i) and (ii) are optionally combined with (iv).

適用之其他電極材料尤其是選自石墨及碳化矽。該塗層可為一種浸漬類型或可為膜，其中該膜或塗層可具有0.01至400 mm，尤其是0.01 mm至200 mm，較佳為0.01至100 mm之厚度。此塗層可為可為電極主體之外塗層及/或可為可於構造程序中供應之數層內塗層及外塗層其中之一。因此，該電極或電極之組件可包含數層由含矽材料之塗層所分開的不同層。該等層可由其他電極材料製成。其他電極材料之基質中的此等其他部分(尤其是選自石墨及/或碳化矽)可包含圓柱、多面體部分、錐形部分、顆粒、丸粒、棒狀、圓柱形棒、粉末、柵、格子、格柵、立方部分及/或粒。 Other electrode materials which are suitable are, in particular, selected from the group consisting of graphite and tantalum carbide. The coating may be of a type of impregnation or may be a film, wherein the film or coating may have a thickness of from 0.01 to 400 mm, especially from 0.01 mm to 200 mm, preferably from 0.01 to 100 mm. The coating can be one that can be an outer coating of the electrode body and/or can be one of several inner coatings and outer coatings that can be supplied in the construction process. Thus, the electrode or electrode assembly can comprise several layers of different layers separated by a coating of the cerium-containing material. The layers can be made of other electrode materials. Such other portions of the matrix of other electrode materials (especially selected from the group consisting of graphite and/or tantalum carbide) may comprise cylinders, polyhedral portions, tapered portions, particles, pellets, rods, cylindrical rods, powders, grids, Grid, grid, cube and/or grain.

根據本發明其他具體實例，該電極包含(i)碳化矽產物及(ii)矽產物，其中其各獨立含有100 ppm(w/w)之Al或更少。尤其是，該碳化矽產物及該矽產物各含有少於80 ppm(w/w)。較佳係該碳化矽產物及該矽產物各獨立含有少於50 ppm(w/w)，更佳為少於10 ppm(w/w)之Al，尤其是少於1 ppm(w/w)之Al，及少於1 ppm(w/w)之Fe，最佳為少於0.5 ppm(w/w)之Al及少於0.5 ppm(w/w)之Fe。 According to other embodiments of the invention, the electrode comprises (i) a cerium carbide product and (ii) a cerium product, each of which independently contains 100 ppm (w/w) Al or less. In particular, the niobium carbide product and the niobium product each contain less than 80% Ppm(w/w). Preferably, the niobium carbide product and the niobium product each independently contain less than 50 ppm (w/w), more preferably less than 10 ppm (w/w) Al, especially less than 1 ppm (w/w). Al, and less than 1 ppm (w/w) Fe, is preferably less than 0.5 ppm (w/w) Al and less than 0.5 ppm (w/w) Fe.

根據本發明一具體實例，該電極或該電極之至少一組件包括含有等於或少於1.5 ppm(w/w)之銀(Ag)的含矽材料。其中，另外較佳情況係該含矽材料含有少於100 ppm(w/w)之鋁，尤其是少於50 ppm(w/w)，較佳為少於35 ppm(w/w)。 According to an embodiment of the invention, the electrode or at least one component of the electrode comprises a cerium-containing material containing silver (Ag) equal to or less than 1.5 ppm (w/w). Preferably, the niobium containing material contains less than 100 ppm (w/w) aluminum, especially less than 50 ppm (w/w), preferably less than 35 ppm (w/w).

根據本發明之較佳具體實例，該電極或該電極之至少一組件包括含矽材料，其中該碳化矽產物及矽產物中之所有其他金屬(排除矽)的總和分別少於100 ppm(w/w)，其中尤其是該等其他金屬係選自Ag、Al、As、Au、Ba、Be、Bi、Ca、Cd、Ce、Co、Cr、Cs、Cu、Dy、Er、Eu、Fe、Ga、Gd、Ge、Hf、Hg、Ho、In、Ir、K、La、Li、Lu、Mg、Mn、Mo、Na、Nb、No、Os、Pb、Pd、Pr、Pt、Rb、Re、Rh、Ru、Sb、Sc、Se、Sm、Sn、Ta、Tb、Te、Th、Ti、Tl、Tm、U、W、Y、Yb、Zn、Zr，或其中所有其他金屬之總和少於80 ppm(w/w)，尤其是少於50 ppm(w/w)，較佳為少於30 ppm(w/w)，更佳為少於10 ppm(w/w)。鐵含量通常低於10 ppm(w/w)。用於偵測該等元素之典型方法為IPC-MS，亦可使用GDMS。 According to a preferred embodiment of the present invention, the electrode or at least one component of the electrode comprises a cerium-containing material, wherein the sum of the cerium carbide product and all other metals in the cerium product (excluding cerium) is less than 100 ppm (w/ w), wherein among these other metals are selected from the group consisting of Ag, Al, As, Au, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga , Gd, Ge, Hf, Hg, Ho, In, Ir, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, No, Os, Pb, Pd, Pr, Pt, Rb, Re, Rh , Ru, Sb, Sc, Se, Sm, Sn, Ta, Tb, Te, Th, Ti, Tl, Tm, U, W, Y, Yb, Zn, Zr, or the sum of all other metals therein is less than 80 ppm (w/w), especially less than 50 ppm (w/w), preferably less than 30 ppm (w/w), more preferably less than 10 ppm (w/w). The iron content is usually below 10 ppm (w/w). A typical method for detecting these elements is IPC-MS, and GDMS can also be used.

在本發明一具體實例中，該電極或該電極之至少一組 件包括含矽材料，其中該含矽材料包含等於或少於1.5 ppm(w/w)之銀，尤其是少於0.1 ppm(w/w)之銀，尤其是少於1.0 ppm(w/w)之硼(B)，較佳為少於0.5 ppm(w/w)，較佳為少於0.35 ppm(w/w)及/或少於2.5 ppm(w/w)之磷(P)，尤其是等於或少於2.0 ppm(w/w)之磷，較佳係少於0.5 ppm(w/w)之P，及隨意的等於或少於5 ppm(w/w)之硫(S)，尤其是少於4.5 ppm(w/w)之硫，較佳為少於0.1 ppm(w/w)之S。 In an embodiment of the invention, the electrode or at least one of the electrodes The article comprises a cerium-containing material, wherein the cerium-containing material comprises silver equal to or less than 1.5 ppm (w/w), especially less than 0.1 ppm (w/w) silver, especially less than 1.0 ppm (w/w Boron (B), preferably less than 0.5 ppm (w/w), preferably less than 0.35 ppm (w/w) and/or less than 2.5 ppm (w/w) of phosphorus (P), In particular, phosphorus equal to or less than 2.0 ppm (w/w), preferably less than 0.5 ppm (w/w) P, and optionally equal to or less than 5 ppm (w/w) sulfur (S) In particular, less than 4.5 ppm (w/w) sulfur, preferably less than 0.1 ppm (w/w) S.

在本發明一具體實例中，該電極或該電極之至少一組件包括含矽材料，其中該含矽材料包含等於或少於：a.鋁(Al)30 ppm(w/w)或為25至0.0001 ppt(w/w)，尤其是22 ppm(w/w)至0.0001 ppt(w/w)，及b.硼(B)1.0 ppm(w/w)至0.0001 ppt(w/w)，尤其是0.5 ppm(w/w)至0.0001 ppt(w/w)，較佳為0.4 ppm(w/w)至0.0001 ppt(w/w)，或特佳為0.35 ppm(w/w)至10 ppb(w/w)；及c.鈣(Ca)20 ppm(w/w)，尤其是15至0.0001 ppt(w/w)，較佳為10 ppm(w/w)至0.0001 ppt(w/w)；及隨意的d.鎵(Ga)1 ppm，尤其是0.5 ppm至0.0001 ppt(w/w)，較佳為0.1 ppm(w/w)至0.0001 ppt(w/w)，尤佳為1 ppb(w/w)至0.0001 ppt(w/w)，e.鎳(Ni)10 ppm(w/w)，尤其是5 ppm(w/w)至0.0001 ppt(w/w)，較佳為3.5 ppm及0.0001 ppt(w/w)； f.磷(P)3 ppm(w/w)至0.0001 ppt(w/w)，尤其是2 ppm(w/w)至0.0001 ppt(w/w)，較佳為1 ppm(w/w)至0.0001 ppt(w/w)，及g.鈦(Ti)2 ppm(w/w)，尤其是1.7 ppm(w/w)至0.0001 ppt，較佳為1.5至0.0001 ppt(w/w)；及h.鋅(Zn)30 ppm(w/w)，尤其是25 ppm(w/w)至0.0001 ppt(w/w)，較佳為10 ppm至0.0001 ppt(w/w)。 In one embodiment of the invention, the electrode or at least one component of the electrode comprises a germanium containing material, wherein the germanium containing material comprises equal to or less than: a. aluminum (Al) 30 ppm (w/w) or 25 to 0.0001 ppt(w/w), especially 22 ppm(w/w) to 0.0001 ppt(w/w), and b. boron (B) 1.0 ppm(w/w) to 0.0001 ppt(w/w), especially It is 0.5 ppm (w/w) to 0.0001 ppt (w/w), preferably 0.4 ppm (w/w) to 0.0001 ppt (w/w), or particularly preferably 0.35 ppm (w/w) to 10 ppb (w/w); and c. calcium (Ca) 20 ppm (w/w), especially 15 to 0.0001 ppt (w/w), preferably 10 ppm (w/w) to 0.0001 ppt (w/w) And optionally d. gallium (Ga) 1 ppm, especially 0.5 ppm to 0.0001 ppt (w/w), preferably 0.1 ppm (w/w) to 0.0001 ppt (w/w), especially preferably 1 Ppb (w/w) to 0.0001 ppt (w/w), e. nickel (Ni) 10 ppm (w/w), especially 5 ppm (w/w) to 0.0001 ppt (w/w), preferably 3.5 ppm and 0.0001 ppt (w/w); f. phosphorus (P) 3 ppm (w/w) to 0.0001 ppt (w/w), especially 2 ppm (w/w) to 0.0001 ppt (w/w), preferably 1 ppm (w/w) To 0.0001 ppt (w/w), and g. titanium (Ti) 2 ppm (w/w), especially 1.7 ppm (w/w) to 0.0001 ppt, preferably 1.5 to 0.0001 ppt (w/w); And h. zinc (Zn) 30 ppm (w/w), especially 25 ppm (w/w) to 0.0001 ppt (w/w), preferably 10 ppm to 0.0001 ppt (w/w).

根據本發明其他實施樣態，該設備組件或該含矽材料包括包含以下者之組成物：(i)含有碳化矽粒子(尤其是作為粉末及/或粒狀)之碳化矽產物，其中該等粒子範圍特別為0.001 μm至10 cm，為0.0001 mm至50 mm，為0.001 mm至25 mm，為0.0001 mm至10 mm，較佳為0.001 mm至5 mm，更佳為0.001 mm至2.5 mm；及隨意的(ii)含有矽粒子(尤其是作為粉末及/或粒狀)之矽產物，其中該等粒子範圍特別為0.001 μm至10 cm，為0.0001 mm至50 mm，為0.001 mm至25 mm，為0.0001 mm至10 mm，較佳為0.001 μm至5 μm，更佳為10 nm至2.5 μm，最佳為10 nm至0.2 μm(見圖4、5及6)。 According to other embodiments of the present invention, the apparatus component or the cerium-containing material comprises a composition comprising: (i) a cerium carbide product comprising cerium carbide particles, especially as a powder and/or granules, wherein The particle range is particularly from 0.001 μm to 10 cm, from 0.0001 mm to 50 mm, from 0.001 mm to 25 mm, from 0.0001 mm to 10 mm, preferably from 0.001 mm to 5 mm, more preferably from 0.001 mm to 2.5 mm; Optionally (ii) a cerium product comprising cerium particles, especially as a powder and/or granules, wherein the particles range in particular from 0.001 μm to 10 cm, from 0.0001 mm to 50 mm, from 0.001 mm to 25 mm, It is from 0.0001 mm to 10 mm, preferably from 0.001 μm to 5 μm, more preferably from 10 nm to 2.5 μm, most preferably from 10 nm to 0.2 μm (see Figures 4, 5 and 6).

根據本發明之較佳具體實例，該設備組件或該含矽材料包含矽粉末作為(ii)矽產物，其中原粒子為10 nm至300 nm，較佳為100至200 nm且二次粒子為0.5至10 μm，較佳為2至5 μm。因此，矽產物包含100至200 nm之原粒子及2至5 μm之二次粒子。該矽產物之結晶度高於95%。此外，該矽產物之比表面為9至12 m²/g，體密度為 0.08至1.0 g/cm³，視產物而定。該矽產物之純度可根據表4或5： According to a preferred embodiment of the invention, the apparatus component or the cerium-containing material comprises cerium powder as (ii) cerium product, wherein the primary particles are from 10 nm to 300 nm, preferably from 100 to 200 nm and the secondary particles are 0.5. Up to 10 μm, preferably 2 to 5 μm. Therefore, the ruthenium product contains primary particles of 100 to 200 nm and secondary particles of 2 to 5 μm. The cerium product has a crystallinity of more than 95%. Further, the niobium product has a specific surface area of 9 to 12 m ² /g and a bulk density of 0.08 to 1.0 g/cm ³ depending on the product. The purity of the hydrazine product can be according to Table 4 or 5:

該矽產物之較佳純度為99.9999%，金屬(包括鐵)少於0.5 ppma，碳少於10 ppma，氧少於10 ppma。純度：>99.9999%，金屬(包括鐵)<0.5 ppma，碳<10 ppma。 The ruthenium product preferably has a purity of 99.9999%, a metal (including iron) of less than 0.5 ppma, a carbon of less than 10 ppma, and an oxygen of less than 10 ppma. Purity: >99.9999%, metal (including iron) <0.5 ppma, carbon <10 ppma.

在本發明一具體實例中，該組件或該含矽材料包括包含以下者之組成物：(i)含有碳化矽粒子之碳化矽產物，其中超過50重量%具有等於或大於0.15 mm之粒度，尤其是等於或超過25重量%該等粒子具有等於或大於0.70 mm之粒度，較佳係等於或超過30重量%，特佳係等於或超過40重量%具有約0.71 mm至約0.15 mm之粒度，及隨意地(ii)含有矽粒子之矽產物，其中超過50重量%具有等於或大於0.15 mm之粒度，尤其是等於或超過25重量%該等粒子具有等於或大於0.70 mm之粒度，較佳係等於或超 過30重量%，特佳係等於或超過40重量%具有約0.71 mm至約0.15 mm之粒度。 In a specific embodiment of the invention, the component or the ruthenium-containing material comprises a composition comprising: (i) a ruthenium carbide product containing ruthenium carbide particles, wherein more than 50% by weight has a particle size equal to or greater than 0.15 mm, in particular Is equal to or more than 25% by weight of the particles having a particle size equal to or greater than 0.70 mm, preferably equal to or more than 30% by weight, particularly preferably equal to or more than 40% by weight, having a particle size of from about 0.71 mm to about 0.15 mm, and Optionally (ii) a cerium product comprising cerium particles, wherein more than 50% by weight has a particle size equal to or greater than 0.15 mm, in particular equal to or more than 25% by weight, the particles have a particle size equal to or greater than 0.70 mm, preferably equal to Or super Over 30% by weight, particularly preferably equal to or more than 40% by weight, has a particle size of from about 0.71 mm to about 0.15 mm.

在本發明一具體實例中，該設備組件之未淬火體，尤其是該爐體或電極之襯裡或該未淬火電極之該至少組件包括具有包含以下者之組成物的含矽材料：(i)含有碳化矽粒子之碳化矽產物，其中超過50重量%具有等於或大於0.15 mm之粒度，尤其是等於或超過25重量%該等粒子具有等於或大於0.70 mm之粒度，較佳係等於或超過30重量%，特佳係等於或超過40重量%具有約0.71 mm至約0.15 mm之粒度。 In a specific embodiment of the invention, the unquenched body of the apparatus component, particularly the lining of the furnace body or electrode or the at least component of the unquenched electrode comprises a bismuth-containing material having a composition comprising: (i) a niobium carbide product containing niobium carbide particles, wherein more than 50% by weight has a particle size equal to or greater than 0.15 mm, especially equal to or more than 25% by weight. The particles have a particle size equal to or greater than 0.70 mm, preferably equal to or more than 30. The % by weight, particularly preferably equal to or more than 40% by weight, has a particle size of from about 0.71 mm to about 0.15 mm.

該等碳化矽粒子以及該等矽粒子為多晶固體或非晶形，尤其是其獨立為多晶固體。在回火及/或加熱程序期間，結晶相之晶域將生長，例如將黏附於其他晶域。在回火及/或加熱期間，該含矽材料的安定性因沉降、生長及/或燒結程序而提高。 The niobium carbide particles and the niobium particles are polycrystalline solid or amorphous, in particular they are independently polycrystalline solids. During the tempering and/or heating process, the crystalline domains of the crystalline phase will grow, for example, will adhere to other crystalline domains. During tempering and/or heating, the stability of the niobium containing material is enhanced by settling, growth and/or sintering procedures.

在本發明一具體實例中，該設備組件，尤其是該還原爐體之內部襯裡、澆斗、電極或該電極之該至少組件包含結晶矽(尤其是多晶矽，較佳係粉末狀結晶矽)作為該矽產物(ii)，尤其是該未淬火電極或其至少一組件。在本發明第二具體實例中，該設備之組件(作為加熱體)，尤其是該還原爐體之內部襯裡、澆斗、該電極或該電極之至少一組件包含氮化矽及隨意的矽作為該矽產物(ii)，尤其是該爐電極或其至少一組件。尤佳情況係該矽產物係至少部分反應成氮化矽，較佳為5至100重量%氮化矽及0至95重量 %之該矽，其中其總和為100重量%，尤佳為20至100重量%氮化矽及80至0重量%之矽，更佳為50至100重量%氮化矽及50至0重量%之矽，最佳為80至100重量%氮化矽及20至0重量%之矽。根據本發明之尤佳具體實例，該矽產物(尤其是該設備組件中，尤其是該還原爐體之內部襯裡、澆斗、爐電極及其至少一組件中之矽產物)包含90至100重量%之氮化矽及10至0重量%之矽，95至100重量%氮化矽及5至100重量%之矽，98至100重量%氮化矽及2至0重量%之矽，尤其是具有上述純度。 In an embodiment of the invention, the apparatus component, in particular the inner lining, the bucket, the electrode or the at least component of the electrode of the reduction furnace body comprises crystalline ruthenium (especially polycrystalline ruthenium, preferably powdered crystalline ruthenium) as The niobium product (ii), in particular the unquenched electrode or at least one component thereof. In a second embodiment of the invention, the assembly of the apparatus (as a heating body), in particular the inner liner of the reduction furnace body, the bucket, the electrode or at least one component of the electrode comprises tantalum nitride and a random crucible The niobium product (ii) is especially the furnace electrode or at least one component thereof. More preferably, the ruthenium product is at least partially reacted into ruthenium nitride, preferably from 5 to 100% by weight of lanthanum nitride and from 0 to 95 parts by weight. % of the yttrium, wherein the sum is 100% by weight, particularly preferably 20 to 100% by weight of lanthanum nitride and 80 to 0% by weight of lanthanum, more preferably 50 to 100% by weight of lanthanum nitride and 50 to 0% by weight Thereafter, it is preferably 80 to 100% by weight of tantalum nitride and 20 to 0% by weight of ruthenium. According to a particularly preferred embodiment of the invention, the niobium product (especially in the equipment assembly, in particular the inner lining of the reduction furnace body, the bucket, the furnace electrode and the tantalum product thereof in at least one of the components) comprises from 90 to 100 weight % of tantalum nitride and 10 to 0% by weight, 95 to 100% by weight of tantalum nitride and 5 to 100% by weight, 98 to 100% by weight of tantalum nitride and 2 to 0% by weight of ruthenium, especially Has the above purity.

此外，在本發明一具體實例中，該電極或該電極之至少一組件包含一層石墨或碳搗製糊，其係配置在螺紋接管及該電極之間。 Moreover, in one embodiment of the invention, the electrode or at least one component of the electrode comprises a layer of graphite or carbon crucible paste disposed between the nipple and the electrode.

根據本發明另一實施樣態，該設備組件(尤其是該還原爐體之內部襯裡、澆斗、該電極或該電極之至少一組件，尤其是該未淬火電極或該未淬火電極之至少一組件)包括具有包含黏結劑之組成物的，其中該黏結劑為選自合成酚-甲醛樹脂之樹脂，或該黏結劑係已知為用於藥學調配物之黏結劑的黏結劑。尤其是，該黏結劑可選自碳水化合物或聚乙烯吡咯啶酮。該等碳水化合物可選自醣、雙醣、單醣、纖維素、羥丙甲基纖維素(HPMC)、甲基纖維素，尤其是蔗糖、乳糖、甘露醇、糊精(dectrin)、右旋糖、微晶型纖維素、纖維素醚、澱粉。 According to another embodiment of the present invention, the apparatus component (especially at least one component of the inner lining, the bucket, the electrode or the electrode of the reduction furnace body, in particular at least one of the unquenched electrode or the unquenched electrode) The component) includes a composition having a binder, wherein the binder is a resin selected from the group consisting of synthetic phenol-formaldehyde resins, or the binder is a binder known as a binder for a pharmaceutical formulation. In particular, the binder may be selected from the group consisting of carbohydrates or polyvinylpyrrolidone. The carbohydrates may be selected from the group consisting of sugars, disaccharides, monosaccharides, cellulose, hydroxypropylmethylcellulose (HPMC), methylcellulose, especially sucrose, lactose, mannitol, dectrin, dextrin Sugar, microcrystalline cellulose, cellulose ether, starch.

此外，該設備之組件(尤其是該還原爐體之內部襯裡、澆斗、該電極或該電極之至少一組件)必須承受碳熱 還原之高溫，且本發明人已選擇該電極之組件或該電極之至少一組件，因而選擇其比例。如此，(i)80-95%(w/w)，較佳為85-95%(w/w)，更佳為87-93%(w/w)之該組件或該電極或該電極之至少一組件的該含矽材料係由該碳化物產物所構成。該碳化物產物含有1.5 ppm(w/w)或更少，較佳為1.0 ppm(w/w)或更少，更佳為0.5 ppm(w/w)，少於0.35 ppm(w/w)之硼或更少，最佳為0.2 ppm(w/w)或更少之B，較佳為0.1 ppm(w/w)至0.0001 ppt(w/w)。此外，該碳化物產物含有3.0 ppm(w/w)或更少，較佳為2.0 ppm(w/w)或更少，更佳為1.0 ppm(w/w)或更少，最佳為0.5 ppm(w/w)或更少之磷，較佳為0.1 ppm(w/w)至0.0001 ppt(w/w)。組成物的總和為100%(w/w)。 Furthermore, the components of the apparatus (especially the inner lining of the reduction furnace, the bucket, the electrode or at least one component of the electrode) must withstand the heat of the carbon The high temperature of the reduction, and the inventors have selected the assembly of the electrode or at least one component of the electrode, and thus the ratio thereof. Thus, (i) 80-95% (w/w), preferably 85-95% (w/w), more preferably 87-93% (w/w) of the component or the electrode or the electrode The at least one component of the cerium-containing material is comprised of the carbide product. The carbide product contains 1.5 ppm (w/w) or less, preferably 1.0 ppm (w/w) or less, more preferably 0.5 ppm (w/w), less than 0.35 ppm (w/w). Boron or less, preferably 0.2 ppm (w/w) or less, preferably 0.1 ppm (w/w) to 0.0001 ppt (w/w). Further, the carbide product contains 3.0 ppm (w/w) or less, preferably 2.0 ppm (w/w) or less, more preferably 1.0 ppm (w/w) or less, most preferably 0.5. Phenol (w/w) or less, preferably from 0.1 ppm (w/w) to 0.0001 ppt (w/w). The sum of the compositions is 100% (w/w).

此外，5-20%(w/w)，較佳為5-15%(w/w)，更佳為7-13%(w/w)之該設備組件(尤其是該還原爐體之內部襯裡、澆斗、該電極或該電極之至少一組件)的含矽材料係由矽產物所構成。該(ii)矽產物含有1.5 ppm(w/w)或更少，較佳為1.0 ppm(w/w)或更少，更佳為0.7 ppm(w/w)或更少，最佳為0.5 ppm(w/w)，較佳為0.35 ppm(w/w)或更少之硼，較佳為0.1 ppm(w/w)至0.0001 ppt(w/w)之硼。此外，該矽產物含有3.0 ppm(w/w)或更少，較佳為2.0 ppm(w/w)或更少，更佳為1.0 ppm(w/w)或更少，最佳為0.5 ppm(w/w)或更少之磷，少於0.2 ppm(w/w)，較佳為0.1 ppm(w/w)至0.0001 ppt(w/w)。 Further, 5-20% (w/w), preferably 5-15% (w/w), more preferably 7-13% (w/w) of the equipment component (especially the interior of the reduction furnace body) The ruthenium-containing material of the liner, the bucket, the electrode or at least one component of the electrode is comprised of a tantalum product. The (ii) hydrazine product contains 1.5 ppm (w/w) or less, preferably 1.0 ppm (w/w) or less, more preferably 0.7 ppm (w/w) or less, most preferably 0.5. Ppm (w/w), preferably 0.35 ppm (w/w) or less, preferably from 0.1 ppm (w/w) to 0.0001 ppt (w/w) of boron. Further, the hydrazine product contains 3.0 ppm (w/w) or less, preferably 2.0 ppm (w/w) or less, more preferably 1.0 ppm (w/w) or less, and most preferably 0.5 ppm. (w/w) or less phosphorus, less than 0.2 ppm (w/w), preferably from 0.1 ppm (w/w) to 0.0001 ppt (w/w).

根據一具體實例，該設備組件(尤其是該還原爐體之 內部襯裡、澆斗、該電極或該電極之至少一組件)之含矽材料的碳化矽產物含有少於100 ppm(w/w)之Al，尤其是少於50 ppm(w/w)，較佳為少於25 ppm(w/w)，少於20 ppm(w/w)，少於15 ppm(w/w)或更少。根據一替代性或互補性具體實例，該電極或該電極之至少一組件之含矽材料的矽產物含有200 ppm(w/w)之Al或更少，諸如100 ppm(w/w)之Al或更少，尤其是50 ppm(w/w)或更少，較佳為25 ppm(w/w)或更少，20 ppm(w/w)或更少，15 ppm(w/w)或更少。 According to a specific example, the equipment component (especially the reduction furnace body) The tantalum carbide product containing the tantalum material of the inner liner, the bucket, the electrode or at least one component of the electrode contains less than 100 ppm (w/w) Al, especially less than 50 ppm (w/w), Preferably less than 25 ppm (w/w), less than 20 ppm (w/w), less than 15 ppm (w/w) or less. According to an alternative or complementary embodiment, the electrode or the tantalum product of the at least one component of the electrode contains 200 ppm (w/w) Al or less, such as 100 ppm (w/w) Al. Or less, especially 50 ppm (w/w) or less, preferably 25 ppm (w/w) or less, 20 ppm (w/w) or less, 15 ppm (w/w) or less.

黏結劑能將內部襯裡的組件結合在一起。此外，該等組件(諸如該還原爐體及/或電極或該電極組成物的部分)在高溫(諸如高於2000℃之溫度)下應安定。樹脂係特別適於此等目的之黏結劑。該樹脂較佳為合成樹脂，諸如通常可具有比天然樹脂更高純度的樹脂，且該樹脂不應包含可相當程度地污染該矽產物的元素。該樹脂可為例如合成酚-甲醛樹脂。具有令人滿意結果的合成樹脂的一特定實例為酚醛清漆(Novolack)。適用樹脂的其他實例為酚醛樹脂(Resol)及Peracit。然而，本發明人暸解亦可使用其他樹脂。根據一具體實例，該電極或該電極之部分的熱傳導率在1500℃下為至少15 W/m°K(克氏溫度)，較佳為在高於900℃之溫度下低於12 W/m°K的熱傳導率。 The binder bonds the components of the inner lining together. In addition, the components, such as the reduction furnace body and/or the electrode or portions of the electrode composition, should be stabilized at elevated temperatures, such as temperatures above 2000 °C. Resins are particularly suitable as binders for these purposes. The resin is preferably a synthetic resin such as a resin which generally has a higher purity than a natural resin, and the resin should not contain an element which can contaminate the niobium product to a considerable extent. The resin may be, for example, a synthetic phenol-formaldehyde resin. A specific example of a synthetic resin having satisfactory results is a novolack. Other examples of suitable resins are phenolic resins (Resol) and Peracit. However, the inventors know that other resins can also be used. According to a specific example, the electrode or portion of the electrode has a thermal conductivity of at least 15 W/m°K (Kelvin temperature) at 1500 ° C, preferably less than 12 W/m at a temperature higher than 900 ° C. The thermal conductivity of °K.

本發明之特定實施樣態為一種用於藉由碳熱還原來製造矽的方法，其中形成包含以下者之未淬火組件且隨意地將它固化：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之 硼，及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(iii)0.1-5%(w/w)之黏結劑，諸如樹脂，例如合成樹脂；且其中此組成物的總和為100%(w/w)。 A particular embodiment of the invention is a method for making tantalum by carbothermal reduction wherein an unquenched component comprising the following is formed and optionally cured: (i) 80-95% (w/w) Contains 1.5 ppm (w/w) or less Boron, and 3.0 ppm (w/w) or less of phosphorus tantalum carbide product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 ppm ( a w/w) or less phosphorus antimony product; and (iii) 0.1-5% (w/w) of a binder such as a resin such as a synthetic resin; and wherein the sum of the compositions is 100% (w/ w).

較佳方法包括下列步驟： The preferred method includes the following steps:

(i)固化所形成之未淬火組件，及隨意地 (i) the unquenched component formed by curing, and optionally

(ii)將該未淬火組件回火，及隨意地 (ii) tempering the unquenched component, and optionally

(iii)加熱該未淬火組件，其中步驟(ii)之溫度高於步驟(i)，且步驟(iii)之溫度高於步驟(ii)。 (iii) heating the unquenched component wherein the temperature of step (ii) is higher than step (i) and the temperature of step (iii) is higher than step (ii).

尤其是該固化、回火及/或加熱係於如氬之惰性氣體之氛圍中進行。此外，該固化、回火及/或加熱可在含有氮之氛圍中進行，尤其是該加熱步驟係在含氮氛圍中進行，較佳係在氮氛圍中進行，例如0.01至100體積%，尤其是10至100體積%之N₂及100體積%之惰性氣體(尤其是氬)，較佳為30至100體積%之N₂及100體積%之惰性氣體中進行。在該程序期間，該矽與該氮反應，及該反應的產物之一為氮化矽Si₃N₄。在本發明之較佳具體實例中，幾乎所有矽產物成為氮化矽。在回火及/或加熱程序期間，碳化矽及氮化矽可一起生長及黏附。此步驟與該組件之隨後的安定性相尤其關。 In particular, the curing, tempering and/or heating is carried out in an atmosphere such as an inert gas of argon. Furthermore, the curing, tempering and/or heating can be carried out in an atmosphere containing nitrogen, in particular the heating step is carried out in a nitrogen-containing atmosphere, preferably in a nitrogen atmosphere, for example from 0.01 to 100% by volume, in particular It is carried out in an inert gas of 10 to 100% by volume of N ₂ and 100% by volume of inert gas (especially argon), preferably 30 to 100% by volume of N ₂ and 100% by volume. During this procedure, the hydrazine reacts with the nitrogen, and one of the products of the reaction is cerium nitride Si ₃ N ₄ . In a preferred embodiment of the invention, substantially all of the niobium product becomes tantalum nitride. During the tempering and/or heating process, tantalum carbide and tantalum nitride can grow and adhere together. This step is particularly relevant to the subsequent stability of the component.

較佳者為由包含以下者之組成物所構成的未淬火組件：(i)85-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及 3.0 ppm(w/w)或更少之磷的碳化矽產物，該等雜質各較佳係少於0.2 ppm(w/w)；(ii)5-15%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物，該等雜質各較佳係少於0.2 ppm(w/w)；及(iii)0.1-2%(w/w)之黏結劑，如樹脂，例如合成樹脂；及其中該組成物於固化前的總合為100%(w/w)。 Preferably, it is an unquenched component consisting of a composition comprising: (i) 85-95% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus tantalum carbide product, preferably less than 0.2 ppm (w/w); (ii) 5-15% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus, preferably less than 0.2 ppm (w/w); and (iii) 0.1- 2% (w/w) of a binder such as a resin such as a synthetic resin; and a total of the composition before curing is 100% (w/w).

根據本發明方法之一其他具體實例，該等數個步驟期間的溫度係受控制。製程參數相當敏感。較佳係(i)在固化步驟期間之溫度為0至300℃，尤其是50至300℃，較佳為100至250℃，特佳為150至250℃，各±25℃，較佳為±5℃，及隨意的(ii)在回火步驟期間之溫度為200至500℃，尤其是200至450℃，較佳為250至400℃，各±25℃，較佳為±5℃，及隨意的(iii)在加熱步驟期間之溫度為350至1400℃，尤其是在數個步驟中之溫度為400至600℃或為600℃至1400℃，或為600至900℃及為900至1400℃，尤其是其中該溫度設定為+5℃/小時，尤其是在步驟(i)、(ii)及/或(iii)中為+10℃/小時或+15℃/小時。 According to other embodiments of one of the methods of the invention, the temperature during the plurality of steps is controlled. Process parameters are quite sensitive. Preferably, (i) the temperature during the curing step is from 0 to 300 ° C, especially from 50 to 300 ° C, preferably from 100 to 250 ° C, particularly preferably from 150 to 250 ° C, each ± 25 ° C, preferably ± 5 ° C, and optionally (ii) during the tempering step, the temperature is 200 to 500 ° C, especially 200 to 450 ° C, preferably 250 to 400 ° C, each ± 25 ° C, preferably ± 5 ° C, and Optionally (iii) the temperature during the heating step is 350 to 1400 ° C, especially in several steps, the temperature is 400 to 600 ° C or 600 ° C to 1400 ° C, or 600 to 900 ° C and 900 to 1400 °C, especially where the temperature is set to +5 ° C / hour, especially in steps (i), (ii) and / or (iii) is +10 ° C / hour or + 15 ° C / hour.

其他製程參數為該等步驟之時段。尤其是於(i)、(ii)及/或(iii)各步驟中之保持時間獨立地為10至250小時，尤其是每一步驟之保持時間為25至150小時，較佳為50至100小時，尤其是步驟(i)及(ii)。尤其是，該方法可以+5℃/小時、+10℃/小時、+15℃/小時、20℃/小時、25℃/小時或30℃/小時之溫度上升來進行，其中因黏結劑之分解程序之故，該等溫度上升係+1至15℃/小時為佳。因此， 較佳為該溫度係以+5℃/小時提高，或最佳係以10℃/小時提高。在後續加熱程序期間，亦可能為+15℃/小時。本發明之典型程序將如下表6所示。 Other process parameters are the time periods of the steps. In particular, the holding time in each of steps (i), (ii) and/or (iii) is independently from 10 to 250 hours, in particular the holding time per step is from 25 to 150 hours, preferably from 50 to 100. Hours, especially steps (i) and (ii). In particular, the method can be carried out at a temperature rise of +5 ° C / hour, + 10 ° C / hour, + 15 ° C / hour, 20 ° C / hour, 25 ° C / hour or 30 ° C / hour, wherein the decomposition due to the binder For the reason of the procedure, the temperature rise is preferably +1 to 15 ° C / hour. therefore, Preferably, the temperature is increased by +5 ° C / hour, or preferably by 10 ° C / hour. It may also be +15 ° C / hour during the subsequent heating process. A typical procedure of the present invention will be shown in Table 6 below.

設備之典型未淬火組件係選自還原爐體之內部襯裡；SiC爐之內部襯裡；加熱或乾燥烘箱之內部襯裡；製粒、製錠、壓塊設備之內部襯裡；擠出器、電極組件、電極、放液通道、供給通道、放液設備之組件、澆斗、坩堝之內部襯裡；保溫爐之內部襯裡；定向凝固爐之內部襯裡；與石英、碳化矽、矽產物或包含石英、碳化矽、矽產物中任一者之調配物接觸的裝置之襯裡；供給通道之內部襯裡及供給管之內部襯裡。 The typical unhardened component of the equipment is selected from the interior lining of the reduction furnace; the internal lining of the SiC furnace; the internal lining of the heating or drying oven; the internal lining of the granulation, ingot making and briquetting equipment; the extruder, the electrode assembly, Electrode, liquid discharge channel, supply channel, assembly of liquid discharge equipment, internal lining of bucket, crucible; internal lining of holding furnace; internal lining of directional solidification furnace; and quartz, tantalum carbide, niobium product or quartz, niobium carbide The lining of the device in contact with the formulation of any of the tantalum products; the inner lining of the supply channel and the inner lining of the supply tube.

本發明之一其他具體實例為用於製造還原爐之內部襯裡及/或電極或該電極之至少一組件的方法，或藉由本發明之方法獲得之電極或該電極之組件，諸如電極、底部電極、電極股、電極主體、電極螺紋接管、電極閉鎖銷、電極夾片及/或電極安裝座，或該等組件任一者的未淬火體，其中形成且隨意地固化未淬火電極及該未淬火電極之至少一組件。特別是，本發明方法包含下列步驟： A further embodiment of the invention is a method for producing an inner lining of a reduction furnace and/or an electrode or at least one component of the electrode, or an electrode obtained by the method of the invention or a component of the electrode, such as an electrode, a bottom electrode Electrode, electrode body, electrode ferrule, electrode latching pin, electrode clip and/or electrode mount, or an unquenched body of any of the components, wherein the unquenched electrode is formed and optionally cured and the unquenched At least one component of the electrode. In particular, the method of the invention comprises the following steps:

(i)固化該形成之未淬火電極或該未淬火電極的至少一組件，及隨意的 (i) curing the formed unhardened electrode or at least one component of the unquenched electrode, and optionally

(ii)回火該未淬火電極或該未淬火電極的至少一組件，尤其是經固化未淬火電極，及隨意的 (ii) tempering at least one component of the unquenched electrode or the unquenched electrode, especially the cured unquenched electrode, and optionally

(iii)加熱該未淬火電極或該未淬火電極之至少一組件，尤其是經回火電極，其中步驟(ii)之溫度高於步驟 (i)，且步驟(iii)之溫度高於步驟(ii)。 (iii) heating at least one component of the unquenched electrode or the unquenched electrode, in particular a tempered electrode, wherein the temperature of step (ii) is higher than the step (i), and the temperature of step (iii) is higher than step (ii).

根據本發明一具體實例，另外較佳係該未淬火電極之一組件為電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座、電源連接或上述組件之一部分。因此，本發明方法之具體實例當中，在諸如氬之惰性氣體氛圍中進行該固化、回火及/或加熱。 According to an embodiment of the invention, it is further preferred that one of the components of the unquenched electrode is an electrode strand, an electrode body, a nipple, a latching pin, a clip, a heat exchanger, a mount, a power connection or a portion of the above components. Thus, in a specific embodiment of the method of the invention, the curing, tempering and/or heating is carried out in an inert gas atmosphere such as argon.

根據本發明之方法，其中該固化、經回火及/或加熱係在含氮氛圍中進行，尤其是該加熱步驟係在含氮氛圍中進行，較佳係在氮氛圍中進行，例如10至100體積%之N₂及100體積%之惰性氣體，尤其是氬。在該程序期間，該矽與該氮反應，及該反應的產物之一為氮化矽Si₃N₄。在本發明之較佳具體實例中，幾乎所有矽產物成為氮化矽。在回火及/或加熱程序期間，碳化矽及氮化矽可一起生長及黏附。此步驟與該電極之隨後的安定性相尤其關。 The method according to the invention, wherein the curing, tempering and/or heating is carried out in a nitrogen-containing atmosphere, in particular the heating step is carried out in a nitrogen-containing atmosphere, preferably in a nitrogen atmosphere, for example 10 to 100% by volume of N ₂ and 100% by volume of inert gas, especially argon. During this procedure, the hydrazine reacts with the nitrogen, and one of the products of the reaction is cerium nitride Si ₃ N ₄ . In a preferred embodiment of the invention, substantially all of the niobium product becomes tantalum nitride. During the tempering and/or heating process, tantalum carbide and tantalum nitride can grow and adhere together. This step is particularly relevant to the subsequent stability of the electrode.

此外，本發明方法具有一步驟，其中該用於藉由碳熱還原製造液態矽之設備的未淬火組件(尤其是還原爐之內部襯裡及/或電極或該未淬火電極之一組件)係由具有選自以下者之組成物的含矽材料所構成：(i)80-95%(w/w)之含有1.0 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之矽產物(尤其是矽，較佳為矽粉末)，其含有1.0 ppm(w/w)或更少之硼，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)之硼，及1.0 ppm(w/w)或更少之磷，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)；及 (iii)0.1-5%(w/w)之黏結劑，如樹脂，例如合成樹脂；及其中該組成物於固化前的總合為100%(w/w)。 Furthermore, the process of the invention has a step wherein the unquenched component of the apparatus for producing liquid helium by carbothermal reduction (especially the inner lining and/or electrode of the reduction furnace or one of the components of the unquenched electrode) is a cerium-containing material having a composition selected from the group consisting of: (i) 80-95% (w/w) containing 1.0 ppm (w/w) or less of boron and 1.0 ppm (w/w) or Less phosphorus phosphorus niobium product; (ii) 5-20% (w/w) niobium product (especially niobium, preferably niobium powder) containing 1.0 ppm (w/w) or less of boron , especially less than 0.5 ppm (w/w) to 0.1 ppt (w/w) of boron, and 1.0 ppm (w/w) or less of phosphorus, especially less than 0.5 ppm (w/w) to 0.1 Ppt(w/w); and (iii) 0.1 to 5% (w/w) of a binder such as a resin such as a synthetic resin; and a total of the composition before curing is 100% (w/w).

該方法步驟(i)及(ii)尤其關鍵，且建議降低加熱速率。亦應設想此等步驟的保持時間。步驟(iii)可能不是極為關鍵，但應選擇稍微降低之速度。非常重要的是防止於該程序期間該含矽材料糊(尤其是可擠出團)氧化。建議在該爐中填滿氬，以使該氛圍為還原性。當然，該爐應儘可能關閉。 Steps (i) and (ii) of the process are especially critical and it is recommended to reduce the heating rate. The retention time of these steps should also be envisaged. Step (iii) may not be extremely critical, but you should choose a slightly lower speed. It is very important to prevent oxidation of the bismuth-containing material paste (especially extrudable mass) during the process. It is recommended that the furnace be filled with argon to make the atmosphere reductive. Of course, the furnace should be closed as much as possible.

建議當該惰性氣體為900-1000℃(度)及高至1400℃時，從氬切換成氮，以獲得介於所添加之Si金屬及氮之間的牢固結合之氮化物連接(Si₃N₄)。尤其是，在整體加熱程序期間使用氮。 It is recommended to switch from argon to nitrogen when the inert gas is 900-1000 ° C (degrees) and up to 1400 ° C to obtain a strong bond between the added Si metal and nitrogen (Si ₃ N ₄ ). In particular, nitrogen is used during the overall heating process.

該含矽材料(組成物之同義詞)為可擠出團或能連續鑄造，尤其是該含矽材料為可壓實，尤其是該材料可壓實0.1至4倍，較佳為1至2.5，尤佳係約2.4倍(一個維度，其中其他兩個維度保持原樣，見實施例)。 The cerium-containing material (synonym of the composition) is an extrudable mass or can be continuously cast, in particular, the cerium-containing material is compactable, in particular, the material can be compacted by 0.1 to 4 times, preferably 1 to 2.5. The better is about 2.4 times (one dimension, the other two dimensions remain the same, see the example).

其中，上述時間直接取決於欲製造之組件或電極，尤其是保持時間取決於該等部分之尺寸。因此，用於製造電極主體、螺紋接管的時間遠比製造閉鎖銷之時間長。 Wherein, the above time is directly dependent on the component or electrode to be fabricated, and in particular the holding time depends on the size of the parts. Therefore, the time for manufacturing the electrode main body and the nipple is much longer than the time for manufacturing the lock pin.

本發明另一具體實例為電極、底部電極、電極股、電極主體、電極螺紋接管、電極閉鎖銷、電極夾片及/或電極安裝座，及根據一替代實例為藉由本發明方法所獲得的電極之未淬火體、未淬火底部電極、電極股、電極主體、電極螺紋接管、電極閉鎖銷、電極夾片及/或電極安裝座。 Another embodiment of the invention is an electrode, a bottom electrode, an electrode strand, an electrode body, an electrode nip, an electrode latching pin, an electrode clip and/or an electrode mount, and an electrode obtained by the method of the invention according to an alternative example Unhardened body, unquenched bottom electrode, electrode strand, electrode body, electrode nipple, electrode latching pin, electrode clip and/or electrode mount.

本發明一實施樣態為具有選自以下者之組成物的含矽材料(組件之同義詞)的用途：(i)80-95%(w/w)之碳化矽產物，其含有1.5 ppm(w/w)或更少之硼，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)之硼，及1.0 ppm(w/w)或更少之磷，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)； (ii)5-20%(w/w)之矽產物，其含有1.5 ppm(w/w)或更少之硼，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)之硼，及3.0 ppm(w/w)或更少之磷，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)；較佳為矽粉末，及(iii)0至5%(w/w)，尤其是0.1-5%(w/w)之黏結劑，諸如樹脂或碳水化合物，例如合成樹脂及/或蔗糖；及其中此組成物的總和為100%(w/w)，該用途係用於製造電極或電極之組件，尤其是用於製造以下者：(iv)該電極之大型組件，其係選自電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座，電源連接，或(v)用於形成該電極之大型組件的至少一部分之其他電極材料的基質(尤其是選自石墨及/或碳化矽)，該大型組件係選自電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座及電源連接，或(vi)用於形成該電極之大型組件的塗層或塗層之一部分，該大型組件係選自電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座及電源連接，或該等組件的一部分，或(iv)接觸襯裡、密封件、黏著劑及/或結合劑或作為其一部分，彼等尤其是位於選自以下者之該電極的組件上：電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座及電源連接，或(vii)其他電極材料之基質中之該電極的其他組件，該 等電極材料尤其是選自石墨及碳化矽，其形成選自以下者之該電極的至少一個組件：電極股、電極主體、螺紋接管、閉鎖銷、夾片、熱交換器、安裝座及電源連接。 One embodiment of the present invention is the use of a cerium-containing material (synonym for the component) having a composition selected from the group consisting of: (i) 80-95% (w/w) of a cerium carbide product containing 1.5 ppm (w) /w) or less boron, especially less than 0.5 ppm (w/w) to 0.1 ppt (w/w) of boron, and 1.0 ppm (w/w) or less of phosphorus, especially less than 0.5 Ppm (w / w) to 0.1 ppt (w / w); (ii) a 5-20% (w/w) bismuth product containing 1.5 ppm (w/w) or less of boron, especially less than 0.5 ppm (w/w) to 0.1 ppt (w/w) Boron, and 3.0 ppm (w/w) or less of phosphorus, especially less than 0.5 ppm (w/w) to 0.1 ppt (w/w); preferably cerium powder, and (iii) 0 to 5 %(w/w), especially 0.1-5% (w/w) of a binder such as a resin or a carbohydrate such as a synthetic resin and/or sucrose; and the sum of such compositions is 100% (w/w) The use is for the manufacture of components of electrodes or electrodes, in particular for the manufacture of: (iv) large components of the electrode, selected from the group consisting of electrode strands, electrode bodies, nipples, latching pins, clips, a heat exchanger, a mount, a power connection, or (v) a substrate (particularly selected from the group consisting of graphite and/or tantalum carbide) for forming at least a portion of a large component of the electrode, the large component being selected from the group consisting of Electrode strand, electrode body, nipple, latching pin, clip, heat exchanger, mount and power connection, or (vi) part of a coating or coating used to form a large component of the electrode, the large component Selected from electrode strands, electrodes Body, nipple, latching pin, clip, heat exchanger, mount and power connection, or part of such components, or (iv) contact lining, seal, adhesive and/or bonding agent or as part of it, They are in particular components on the electrode selected from the group consisting of electrode strands, electrode bodies, nipples, latching pins, clips, heat exchangers, mounts and power connections, or (vii) substrates of other electrode materials Other components of the electrode, The isoelectric material is, in particular, selected from the group consisting of graphite and tantalum carbide, which forms at least one component of the electrode selected from the group consisting of an electrode strand, an electrode body, a nipple, a latching pin, a clip, a heat exchanger, a mount and a power connection .

因此，本發明之電極可與用於藉由碳熱還原製造液態矽之反應爐體一起使用，該爐體包含內部襯裡，其特徵在於該內部襯裡包含：80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼，及1.0 ppm(w/w)或更少之磷的碳化矽產物；5-20%(w/w)之矽產物，其含有1.5 ppm(w/w)或更少之硼，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)之硼，及1.0 ppm(w/w)或更少之磷，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)；及0-5%(w/w)之黏結劑反應產物，諸如樹脂，例如合成樹脂。 Thus, the electrode of the present invention can be used with a reaction furnace body for the production of liquid helium by carbothermal reduction, the furnace body comprising an inner liner, characterized in that the inner liner comprises: 80-95% (w/w) a niobium carbide product containing 1.5 ppm (w/w) or less of boron, and 1.0 ppm (w/w) or less of phosphorus; 5-20% (w/w) of niobium product containing 1.5 ppm ( W/w) or less boron, especially less than 0.5 ppm (w/w) to 0.1 ppt (w/w) of boron, and 1.0 ppm (w/w) or less of phosphorus, especially less 0.5 ppm (w/w) to 0.1 ppt (w/w); and 0-5% (w/w) of a binder reaction product such as a resin such as a synthetic resin.

根據一具體實例，使用還原爐及/或電極藉由碳熱還原來製造含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物，其包括下列步驟：a)在具有至少一個電極的還原爐中添加二氧化矽、矽石、沉澱矽石、火成矽石及/或含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷(尤其是0.50 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷)的石英產物及包含碳化矽產物、碳水化合物、蔗糖、糖及/或其至少兩者的混合物(尤其是SiC與糖之混合物)的碳源，較佳為含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物或糖；及b)加熱該混合物以形成該矽產物的熔體， 其中該至少一個電極或該至少一個電極的組件包括具有選自以下者之組成物的含矽材料：(I)80-95%(w/w)之具有與步驟a)中所添加之碳化矽產物至少相同純度的碳化矽產物，(ii)5-20%(w/w)之至少具有由該方法所製造之矽產物的純度之矽產物；及(iii)0-5%(w/w)之黏結劑反應產物，如樹脂及/或碳水化合物。 According to a specific example, a ruthenium product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus is produced by carbothermal reduction using a reduction furnace and/or an electrode. The method comprises the steps of: a) adding cerium oxide, vermiculite, precipitated vermiculite, fumed vermiculite and/or containing 1.5 ppm (w/w) or less of boron and 3.0 ppm in a reduction furnace having at least one electrode. Quartz products of (w/w) or less phosphorus (especially 0.50 ppm (w/w) or less of boron and 1.0 ppm (w/w) or less of phosphorus) and inclusion of niobium carbide products, carbohydrates a carbon source of sucrose, sugar and/or a mixture of at least two thereof (especially a mixture of SiC and sugar), preferably containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) Or less phosphorus of the niobium carbide product or sugar; and b) heating the mixture to form a melt of the niobium product, Wherein the at least one electrode or the assembly of the at least one electrode comprises a cerium-containing material having a composition selected from the group consisting of: (I) 80-95% (w/w) having the cerium carbide added in step a) a product of at least the same purity of ruthenium carbide, (ii) 5-20% (w/w) of a ruthenium product having at least the purity of the ruthenium product produced by the process; and (iii) 0-5% (w/w a binder reaction product such as a resin and/or a carbohydrate.

本發明之其他具體實例係選自根據本發明方法所獲得之組件，諸如還原爐體之內部襯裡；SiC爐之內部襯裡；加熱或乾燥烘箱之內部襯裡；製粒、製錠、壓塊設備之內部襯裡；擠出器、電極組件、電極、放液通道、供給通道、放液設備之組件、澆斗、坩堝之內部襯裡；保溫爐之內部襯裡；定向凝固爐之內部襯裡；與石英、碳化矽、矽產物或包含石英、碳化矽、矽產物中任一者之調配物接觸的裝置之襯裡；供給通道之內部襯裡及供給管之內部襯裡；選自電極股、電極主體、螺紋接管、閉鎖銷、夾片、其或電極中任一者之安裝或未淬火體，諸如底部電極或包含至少兩個上述電極組分之電極裝配件。 Further specific examples of the invention are selected from the components obtained according to the process of the invention, such as the internal lining of a reduction furnace body; the internal lining of an SiC furnace; the internal lining of a heating or drying oven; the granulation, ingot making, briquetting equipment Internal lining; extruder, electrode assembly, electrode, draining channel, supply channel, assembly of liquid discharge equipment, internal lining of bucket, crucible; internal lining of holding furnace; internal lining of directional solidification furnace; and quartz, carbonization Lining of the tantalum, niobium product or device comprising the formulation of any of quartz, tantalum carbide, niobium product; inner lining of the supply channel and inner lining of the supply tube; selected from electrode strands, electrode body, nipple, latching An installed or unquenched body of either a pin, a clip, or an electrode thereof, such as a bottom electrode or an electrode assembly comprising at least two of the above electrode components.

另外之具體實例係將一種用於藉由碳熱還原製造液態矽之設備的組件用於藉由碳熱還原製造含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物的用途，該製造包含以下步驟：a)將選自含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷，尤其是0.50 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷的矽石及石英產物之二氧化矽產 物及包括含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物、碳水化合物及/或蔗糖之碳源添加至具有至少一個電極之還原爐；及b)加熱該混合物以形成該矽產物的熔體，其中該還原爐及/或申請專利範圍第1至30項中任一項之組件包含選自以下者之組成物：(i)80-95%(w/w)之具有與步驟a)中所添加之碳化矽產物至少相同純度的碳化矽產物，(ii)5-20%(w/w)之矽產物，尤其是包含氮化矽及隨意的矽，其至少具有由步驟a)及b)所製造之矽產物的純度；及(iii)0-5%(w/w)之黏結劑反應產物，如樹脂或碳水化合物。 Another specific example is a component for an apparatus for producing liquid helium by carbothermal reduction for producing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) by carbothermal reduction. Use of less or less phosphorus ruthenium product, the preparation comprising the steps of: a) being selected from phosphorus containing 1.5 ppm (w/w) or less and 3.0 ppm (w/w) or less, especially Is a 0.50 ppm (w/w) or less boron and 1.0 ppm (w/w) or less phosphorus vermiculite and a quartz product of cerium oxide And a carbon source comprising a niobium carbide product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus, carbohydrates and/or sucrose is added to have at least one electrode a reduction furnace; and b) heating the mixture to form a melt of the bismuth product, wherein the reduction furnace and/or the assembly of any one of claims 1 to 30 comprises a composition selected from the group consisting of: (i 80-95% (w/w) of a niobium carbide product having at least the same purity as the niobium carbide product added in step a), (ii) 5-20% (w/w) of the niobium product, especially comprising Tantalum nitride and random tantalum having at least the purity of the tantalum product produced by steps a) and b); and (iii) 0-5% (w/w) of binder reaction product such as resin or carbohydrate .

其他具體實例係用於藉由碳熱還原製造含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物之方法，其包括下列步驟：a)將含有0.50 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷的石英產物及含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷之碳化矽產物添加至具有內部襯裡之還原爐；及b)加熱該混合物以形成該矽產物的熔體，其中該襯裡包含：80-95%(w/w)之具有與步驟a)中所添加之碳化矽產物相同純度的碳化矽產物；5-20%(w/w)之至少具有由該方法所製造之矽產物的純度之矽產物；及0.1-5%(w/w)之黏結劑或黏結劑反應產物，如樹脂。 Other specific examples are methods for producing a ruthenium product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus by carbothermal reduction, which comprises the steps of: a a quartz product containing 0.50 ppm (w/w) or less of boron and 1.0 ppm (w/w) or less of phosphorus and containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w) /w) or less of the phosphorus niobium carbide product is added to the reduction furnace having an inner liner; and b) heating the mixture to form a melt of the niobium product, wherein the liner comprises: 80-95% (w/w) a niobium carbide product having the same purity as the niobium carbide product added in step a); 5-20% (w/w) of a niobium product having at least the purity of the niobium product produced by the method; and 0.1-5 %(w/w) of a binder or binder reaction product, such as a resin.

又，提出一種藉由碳熱還原製造含有3.0 ppm(w/w)，較佳為1.5 ppm(w/w)或更少之硼及5.0 ppm (w/w)，較佳為3.0 ppm(w/w)或更少之磷的矽產物的方法，該方法包括下列步驟：a)在具有電極的還原爐中添加二氧化矽、矽石、沉澱矽石、火成矽石及/或石英產物或前述至少兩者的混合物含有0.5 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷及包含碳化矽產物、碳水化合物、蔗糖、糖及/或其至少兩者的混合物(尤其是SiC與糖之混合物)的碳源，較佳為含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物或糖；及b)加熱該混合物以形成該矽產物的熔體，其中該電極或該電極之組件包括具有選自以下者之組成物的含矽材料：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼，及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之矽產物(尤其是氮化矽及隨意的矽)，其含有1.5 ppm(w/w)或更少之硼，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)之硼，及3.0 ppm(w/w)或更少之磷，尤其是少於0.5 ppm(w/w)至0.1 ppt(w/w)之磷；及0-5%(w/w)之黏結劑或黏結劑反應產物，較佳為0%之黏結劑，諸如樹脂，及0至5%(w/w)之該黏結劑反應產物。 Further, it is proposed to produce boron containing 3.0 ppm (w/w), preferably 1.5 ppm (w/w) or less, and 5.0 ppm by carbothermal reduction. (w/w), preferably a method of a phosphorus product of 3.0 ppm (w/w) or less, the method comprising the steps of: a) adding cerium oxide, vermiculite, in a reduction furnace having an electrode, The precipitated vermiculite, fumed vermiculite and/or quartz product or a mixture of at least two of the foregoing contains 0.5 ppm (w/w) or less of boron and 1.0 ppm (w/w) or less of phosphorus and contains niobium carbide The carbon source of the product, carbohydrate, sucrose, sugar and/or a mixture of at least two thereof (especially a mixture of SiC and sugar) preferably contains 1.5 ppm (w/w) or less of boron and 3.0 ppm (of w/w) or less phosphorus tantalum carbide product or sugar; and b) heating the mixture to form a melt of the tantalum product, wherein the electrode or the electrode assembly comprises a composition having a composition selected from the group consisting of Bismuth material: (i) 80-95% (w/w) of niobium carbide containing 1.5 ppm (w/w) or less of boron, and 3.0 ppm (w/w) or less of phosphorus; ) 5-20% (w/w) of barium products (especially tantalum nitride and random germanium) containing 1.5 ppm (w/w) or less of boron, especially less than 0.5 ppm (w/w) ) to 0.1 ppt (w/w) of boron, and 3.0 ppm (w/w) or less of phosphorus, especially less than 0.5 ppm (w) /w) to 0.1 ppt (w/w) of phosphorus; and 0-5% (w/w) of a binder or binder reaction product, preferably 0% of a binder, such as a resin, and 0 to 5% (w/w) of the binder reaction product.

根據下列圖式及一般實施例更詳細說明本發明，但本發明不侷限於該等實施例。 The invention will be described in more detail based on the following drawings and general examples, but the invention is not limited to the embodiments.

發明詳細說明Detailed description of the invention

作為本揭示之第一實施樣態，因此提出一種用於藉由碳熱還原製造液態矽的電極或電極之組件，該電極或該電 極之組件包括含矽產物，其特徵在於該含矽產物包含80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼，及3.0 ppm(w/w)或更少之磷的碳化矽產物；5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及0至6%(w/w)之黏結劑反應物，或在未淬火電極或該電極之未淬火部分中含有0.1-5%(w/w)之黏結劑，諸如樹脂，例如合成酚-甲醛樹脂。 As a first embodiment of the present disclosure, there is therefore proposed an assembly for an electrode or electrode for producing liquid helium by carbothermal reduction, the electrode or the electricity The pole assembly comprises a cerium-containing product characterized in that the cerium-containing product comprises 80-95% (w/w) of boron containing 1.5 ppm (w/w) or less, and 3.0 ppm (w/w) or more. a rare earth carbonized niobium product; 5-20% (w/w) of a niobium product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus; Up to 6% (w/w) of the binder reactant, or 0.1 to 5% (w/w) of a binder, such as a resin, such as a synthetic phenol-formaldehyde resin, in the unquenched electrode or the unquenched portion of the electrode .

於本發明之還原爐及電極中所產生的液態矽可藉由氣體萃取以氯氣精製，其主要移除鋁(Al)、鈣(Ca)及在當時條件下能與該氯氣形成鹽及熔渣的其他元素。硼(B)及磷(P)並非此等元素。該氣體萃取接著可進行藉由定向凝固精製，該期間鐵(Fe)、Al及具有低分布係數之其他金屬因其在熔體中的溶解性較高而從該凝固中的矽分離出。然而，B及P之分布係數相對較高。 The liquid helium produced in the reduction furnace and the electrode of the present invention can be refined by chlorine gas extraction, which mainly removes aluminum (Al), calcium (Ca) and can form salt and slag with the chlorine gas under the current conditions. Other elements. Boron (B) and phosphorus (P) are not such elements. This gas extraction can then be carried out by directional solidification, during which iron (Fe), Al and other metals having a low distribution coefficient are separated from the solidified ruthenium due to their high solubility in the melt. However, the distribution coefficients of B and P are relatively high.

為了補償在上述精製步驟中低效率移除B及P，選擇所提及元素之含量低的起始材料。此外，重要的是在碳熱還原期間該等含量未提高。本發明人已選擇該還原爐之內部襯裡及該電極以及其部分(尤其是與矽熔體直接接觸或雜質因此擴散的所有部分)之組件中的B及P之上限。 In order to compensate for the inefficient removal of B and P in the above refining step, a starting material having a low content of the mentioned elements is selected. Furthermore, it is important that these levels are not increased during the carbothermal reduction. The inventors have selected the upper limits of the internal lining of the reduction furnace and the components B and P in the assembly of the electrode and its parts, especially all of which are in direct contact with the bismuth melt or where the impurities are thus diffused.

因此，該還原爐體可包含經配置以與該內部襯裡之外表面接觸的第二襯裡。如此，在此種具體實例中，該第二襯裡的內表面係與該內部襯裡的外表面接觸。該內部襯裡及第二襯裡可被視為不同保護層。該第二襯裡通常由與該內部襯裡材料不同的耐熱性材料所構成。此種材料之實例 為矽石搗製糊或矽石，其可具有與添加作為該碳熱還原中之起始材料的石英相同純度。 Accordingly, the reduction furnace body can include a second liner configured to contact the outer surface of the inner liner. Thus, in such a specific example, the inner surface of the second liner is in contact with the outer surface of the inner liner. The inner liner and the second liner can be considered as different protective layers. The second liner is typically constructed of a heat resistant material that is different from the inner liner material. An example of such a material For the gangue paste or vermiculite, it may have the same purity as the quartz added as the starting material in the thermal reduction of the carbon.

該碳熱還原所需之能源較佳係由連接至至少兩個電極的電源(諸如DC或AC電源)供應，該等電極經配置以使得在該爐內部電弧可提供熱材料。 The energy required for the carbothermal reduction is preferably supplied by a power source (such as a DC or AC power source) connected to at least two electrodes that are configured such that an arc within the furnace can provide thermal material.

如此，根據一具體實例，本發明之(第一)電極，尤其是由含矽材料所製成的電極係配置成從該爐上方延伸至該爐內部。該爐可例如具有開放式頂部，及該(第一)電極可延伸通過該開口。在一具體實例中，多於一個，諸如二或三個(第一)電極係經配置以從該爐上方延伸至該爐內部。 Thus, according to a specific example, the (first) electrode of the present invention, particularly an electrode system made of a cerium-containing material, is configured to extend from above the furnace to the interior of the furnace. The furnace can, for example, have an open top and the (first) electrode can extend through the opening. In one embodiment, more than one, such as two or three (first) electrodes, are configured to extend from above the furnace to the interior of the furnace.

根據另一具體實例，一或多個(第二)電極係配置成其從該爐下方延伸至該爐底部內，尤其是根據本發明，尤其是由該含矽材料所製成之電極。此種(第二)電極不延伸至可接觸該材料的該爐內部。而是，其一端嵌入該爐之底部(見，例如圖2之206及圖3之306)。根據本發明一實施樣態，該底部電極可由石墨製成且該還原爐之內部襯裡係由該含矽材料製成(組件)，因此具有底部電極之表面積比原有底部電極增加的功用。在此情況下，石墨電極之功用大致為接觸元件的功用。 According to another embodiment, one or more (second) electrode systems are arranged such that they extend from below the furnace into the bottom of the furnace, in particular according to the invention, in particular electrodes made of the cerium-containing material. Such (second) electrodes do not extend into the interior of the furnace where the material can be contacted. Instead, one end is embedded in the bottom of the furnace (see, for example, 206 of Figure 2 and 306 of Figure 3). According to an embodiment of the invention, the bottom electrode can be made of graphite and the inner liner of the reduction furnace is made of the tantalum-containing material (assembly), thus having the effect that the surface area of the bottom electrode is increased compared to the original bottom electrode. In this case, the function of the graphite electrode is roughly the function of the contact element.

該(等)第一及/或第二電極較佳係由含矽材料所構成，或其至少部分係由該含矽材料所構成。隨意地結合其他電極材料(諸如不會污染該液態矽的高純度石墨)的該高純度含矽材料可用於此等應用。在一具體實例中，一層或一塊石墨或碳搗製糊係配置在該爐的內部襯裡及第二襯裡之間 (見例如圖2之203)。較佳地，此層或塊石墨或碳搗製糊係與電極接觸，例如第二電極之上端可嵌入該層或塊石墨或碳搗製糊(見，例如圖2之203及206)。因此該層或塊石墨或碳搗製糊的效果之一係使該電極之表面積增加。 Preferably, the first and/or second electrode is comprised of a ruthenium-containing material, or at least a portion thereof is comprised of the ruthenium-containing material. The high purity niobium containing material optionally combined with other electrode materials such as high purity graphite which does not contaminate the liquid helium can be used for such applications. In one embodiment, one or a layer of graphite or carbon crucible paste is disposed between the inner liner of the furnace and the second liner (See, for example, 203 of Figure 2). Preferably, the layer or block of graphite or carbon paste is in contact with the electrode, for example, the upper end of the second electrode may be embedded in the layer or a block of graphite or carbon paste (see, for example, 203 and 206 of Figure 2). Therefore, one of the effects of the layer or block of graphite or carbon paste is to increase the surface area of the electrode.

在一具體實例中，該還原爐體包含外殼，例如用於25使該爐構造保持在一起。該外殼可例如為該爐構造的最外層(見，例如圖2之204)。如此，若使用第二襯裡，則該外殼較佳係配置在該第二襯裡外部。該外殼可例如由鋼所構成，較佳為非磁性鋼。該爐可配備有旋轉上部分(分離30體)，其可與該爐之下部分獨立地旋轉。該分離體構造可改善該爐中之材料運送及氣體滲透性。此外，一或多個電線圈可配置在該爐內部，以產生磁場以使在該爐內部之電弧旋轉。此種構造使能源在該反應區中分布得更均勻。 In one embodiment, the reduction furnace body includes a casing, such as for 25 to hold the furnace configuration together. The outer casing may for example be the outermost layer of the furnace construction (see, for example, 204 of Figure 2). Thus, if a second liner is used, the outer casing is preferably disposed outside of the second liner. The outer casing may, for example, be constructed of steel, preferably non-magnetic steel. The furnace may be equipped with a rotating upper portion (separation 30 body) that is rotatable independently of the lower portion of the furnace. The separation structure can improve material transport and gas permeability in the furnace. Additionally, one or more electrical coils may be disposed within the furnace to generate a magnetic field to cause arcing within the furnace. This configuration allows the energy to be more evenly distributed in the reaction zone.

此外，可將絕緣層(諸如網或織物)配置在該外殼及第二襯裡之間。除了提供絕緣效果之外，此種層可促進該等襯裡相對於該外殼的移動。此等移動可為例如溫度變化的結果。 Additionally, an insulating layer, such as a mesh or fabric, can be disposed between the outer casing and the second liner. In addition to providing an insulating effect, such a layer promotes movement of the liner relative to the outer casing. Such movements can be, for example, the result of temperature changes.

通常，經由該還原爐之開放式頂部將起始材料進料至其中。此外，所製造之矽液體累積在該還原爐底部。因此，放液通道/流道較佳係設在該爐底部。經由此通道/流道，所製造之矽液體排空至其他隔室(諸如澆斗)以供進一步處理(例如精製)(見例如圖3之302)。該通道較佳可關閉以使得放液可受到控制。 Typically, the starting material is fed into it via the open top of the reduction furnace. In addition, the produced helium liquid accumulates at the bottom of the reduction furnace. Therefore, the drain passage/flow passage is preferably provided at the bottom of the furnace. Through this passage/flow path, the produced helium liquid is vented to other compartments (such as a bucket) for further processing (e.g., refining) (see, for example, 302 of Figure 3). The channel is preferably closable so that the drainage can be controlled.

此通道/流道穿透該爐構造的所有層。然而，該通道/ 流道的內壁較佳係由該內部襯裡所構成，以防止流經該通道/流道的矽液體之污染。該還原爐通常配備有強制冷卻配置。例如，該還原爐可例如藉由空氣或其他冷卻介質(諸如其他氣體)從下方冷卻。本發明人已發現若通過該爐底部的熱傳導率高於9.5 W/°K(通過該爐底部數層的熱傳導率之總和值)，則可獲得充足冷卻效果。 This channel/flow path penetrates all layers of the furnace configuration. However, the channel / The inner wall of the flow passage is preferably constructed of the inner liner to prevent contamination of the helium liquid flowing through the passage/flow passage. The reduction furnace is usually equipped with a forced cooling configuration. For example, the reduction furnace can be cooled from below by, for example, air or other cooling medium such as other gases. The inventors have found that if the thermal conductivity through the bottom of the furnace is higher than 9.5 W/°K (the sum of the thermal conductivities of several layers passing through the bottom of the furnace), sufficient cooling effect can be obtained.

作為第二實施樣態，提出一種用於藉由碳熱還原製造含有1.5 ppm(w/w)或更少之硼，尤其是少於1.0 ppm(w/w)，較佳為少於0.2 ppm(w/w)之硼，及3.0 ppm(w/w)或更少之磷，尤其是少於1.0 ppm(w/w)，較佳為少於0.1 ppm(w/w)之磷的矽產物方法。該方法包括下列步驟：a)將含有0.5 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷之二氧化矽、矽石及/或石英產物及含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳源、碳化矽產物及/或碳水化合物(諸如蔗糖及/或糖)添加至具有內部襯裡及電極之還原爐；及b)加熱該混合物以形成該矽產物的熔體，其中該電極或電極及襯裡包括含有以下者之含矽材料：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼，及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之矽產物，尤其是氮化矽，其含有0.5 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷，尤其是少於1.0 ppm(w/w)，較佳為少於0.1 ppm(w/w)之磷；及0至5%(w/w)，尤其是0%(w/w)之黏結劑，或者0.1-5%(w/w)之黏結劑或其反應產物。 As a second embodiment, a method for producing boron containing 1.5 ppm (w/w) or less, especially less than 1.0 ppm (w/w), preferably less than 0.2 ppm, by carbothermal reduction is proposed. (w/w) boron, and 3.0 ppm (w/w) or less phosphorus, especially less than 1.0 ppm (w/w), preferably less than 0.1 ppm (w/w) phosphorus Product method. The method comprises the steps of: a) a ceria, vermiculite and/or quartz product containing 0.5 ppm (w/w) or less of boron and 1.0 ppm (w/w) or less of phosphorus and containing 1.5 a carbon source of ppm (w/w) or less and a carbon source of 3.0 ppm (w/w) or less of phosphorus, a cerium carbide product and/or a carbohydrate such as sucrose and/or sugar are added to the interior lining and a reduction furnace for the electrode; and b) heating the mixture to form a melt of the niobium product, wherein the electrode or electrode and the liner comprise a niobium containing material comprising: (i) 80-95% (w/w) 1.5 ppm (w/w) or less of boron, and 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5-20% (w/w) of niobium product, especially nitrogen Pupation, which contains 0.5 ppm (w/w) or less of boron and 1.0 ppm (w/w) or less of phosphorus, especially less than 1.0 ppm (w/w), preferably less than 0.1 ppm (w/w) phosphorus; and 0 to 5% (w/w), especially 0% (w/w) of a binder, or 0.1-5% (w/w) of a binder or a reaction product thereof.

在一具體實例中，藉由該方法所製造之矽產物含有1.0 ppm(w/w)或更少之硼及/或2.0 ppm(w/w)或更少之磷。下文探討一些實施樣態之許多其他具體實例的細節。該電極及/或該內部襯裡中之碳化矽產物可例如與步驟a)中所添加之碳化矽產物具有相同品質。如此，該電極及/或該內部襯裡之碳化矽產物可含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷。此碳化矽之製造茲於以下實例參考圖1簡單解釋。如此，可使用單一製造方法提供用於兩種不同但相關之應用的碳化矽。該內部襯裡中的矽產物可為該方法所製造之矽產物的精製版本(此精製係於前文討論)。尤其是，該矽產物可藉由JSSi GmbH Evonik Industries AG及SolarWorld as SUNSil®提供。如此，該電極、該電極之至少一組件及/或該內部襯裡之矽產物可含有0.6 ppm(w/w)或更少之硼及0.8 ppm(w/w)或更少之磷。因此，該方法可用以製造上述該方法中所使用之還原爐的組件。在步驟b)中將該混合物加熱至至少2000℃。可將該爐冷卻，使得1410℃等溫線位於該內部襯裡中之預定位置。 In one embodiment, the ruthenium product produced by the process contains 1.0 ppm (w/w) or less of boron and/or 2.0 ppm (w/w) or less of phosphorus. The details of many other specific examples of some implementations are discussed below. The electrode and/or the niobium carbide product in the inner liner may, for example, be of the same quality as the niobium carbide product added in step a). As such, the electrode and/or the inner liner of the tantalum carbide product may contain 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus. The manufacture of this tantalum carbide is briefly explained with reference to Fig. 1 in the following examples. As such, a single manufacturing process can be used to provide niobium carbide for two different but related applications. The ruthenium product in the inner liner can be a refined version of the ruthenium product produced by the process (this refinement is discussed above). In particular, the niobium product can be supplied by JSSi GmbH Evonik Industries AG and SolarWorld as SUNSil®. As such, the electrode, at least one component of the electrode, and/or the tantalum product of the inner liner may contain 0.6 ppm (w/w) or less of boron and 0.8 ppm (w/w) or less of phosphorus. Therefore, the method can be used to manufacture the components of the reduction furnace used in the above method. The mixture is heated to at least 2000 ° C in step b). The furnace can be cooled such that the 1410 ° C isotherm is at a predetermined location in the inner liner.

實施例Example

下文茲參考圖1描述用於製造太陽能等級矽的範例系統。將來自礦場的天然石英101添加至石英處理設備102，該天然石英於其中經歷以下一或多個步驟：壓碎、篩選、研磨、光學分級、磁力分離、重力分離、浮選及酸 性處理光學分級(包括光學偵測該天然石英中之雜質)。例如，該等雜質可目視為深色斑點。此外，該光學分級可包括去除利用壓縮空氣偵測到具有此等斑點的材料小塊。即，可將此等小塊吹離運送帶，諸如輸送帶等。該酸性處理可包括溶解及去除雜質。在浮選中，將物理化學表面性質不同於石英的材料小塊分離。該磁力分離包括去除含有磁性礦物之材料小塊。 An example system for fabricating a solar grade crucible is described below with reference to FIG. Natural quartz 101 from the mine is added to a quartz processing apparatus 102 where it undergoes one or more of the following steps: crushing, screening, grinding, optical grading, magnetic separation, gravity separation, flotation, and acid Optical processing of optical classification (including optical detection of impurities in the natural quartz). For example, such impurities can be considered as dark spots. Additionally, the optical grading can include removing small pieces of material having such spots detected using compressed air. That is, the pieces can be blown away from the conveyor belt, such as a conveyor belt or the like. The acidic treatment can include dissolving and removing impurities. In the flotation, a small piece of material having a physicochemical surface property different from that of quartz is separated. This magnetic separation involves the removal of small pieces of material containing magnetic minerals.

將來自石英處理設備102之一些石英103添加至碳化矽製造設備105，於其中亦添加高30純度之碳黑104。此種碳黑可為例如從天然氣衍生。在替代實例中，將高純度二氧化矽(例如大於或等於99.9999重量%，排除矽(諸如矽石)之所有金屬的總和<0.005 ppm(w/w))提供於處理設備102。 Some quartz 103 from the quartz processing apparatus 102 is added to the tantalum carbide manufacturing apparatus 105, and carbon black 104 having a high purity of 30 is also added thereto. Such carbon black can be, for example, derived from natural gas. In an alternate example, high purity cerium oxide (eg, greater than or equal to 99.9999% by weight, the sum of all metals excluding cerium (such as vermiculite) < 0.005 ppm (w/w)) is provided to processing device 102.

將來自石英處理設備102相同類型之經處理石英106(或在替代實例中為二氧化矽、矽石)連同來自該系統中之下游位置的再循環矽金屬107及來自碳化矽製造設備105的碳化矽108一起添加至用於秤重及混合之配置109。然後利用加料設備110將該經適當混合的材料添加至還原爐111。添加至該還原爐111之材料中的石英對碳化矽之重量比5為約1.1：1。防煙頭罩112係配置在該還原爐111上方以收集該還原程序期間所形成的氣體。將所收集的氣體經由導管116送至煙道氣過濾及粉塵處理裝置117。該裝置117包含煙囪118，10經純化之氣體通過該煙囪118排出。 Treated quartz 106 of the same type from quartz processing apparatus 102 (or, in the alternative, cerium oxide, vermiculite) along with recycled rhodium metal 107 from downstream locations in the system and carbonization from tantalum carbide manufacturing facility 105 The 矽108 is added together to the configuration 109 for weighing and mixing. The appropriately mixed material is then added to the reduction furnace 111 by the charging device 110. The weight ratio of quartz to tantalum carbide added to the material of the reduction furnace 111 is about 1.1:1. A smoke prevention hood 112 is disposed above the reduction furnace 111 to collect gas formed during the reduction process. The collected gas is sent to the flue gas filtration and dust treatment device 117 via the conduit 116. The apparatus 117 includes a chimney 118 through which the purified gas is discharged.

由含矽材料所構成(尤其是由本發明之組成物所構成)的第一電極113係配置成從上方延伸至該還原爐111內。亦由本發明之含矽材料所構成的第二電極114係配置在該還原爐之底部。第一電極113及第二電極114係連接至電源115(諸如DC或AC電源)，用於產生加熱該碳熱還原程序的電弧。使還原爐114中所形成的矽熔體經由該還原爐114之放液區流出至澆斗119，該澆斗已經由澆斗預熱裝置135預熱。在流出期間，可將惰性氣體(諸如氬)鼓泡通過該澆斗以攪拌其中的矽熔體。可將材料連續添加至該還原爐111。 The first electrode 113 composed of a niobium-containing material (especially composed of the composition of the present invention) is disposed to extend from above into the reduction furnace 111. The second electrode 114, which is also composed of the cerium-containing material of the present invention, is disposed at the bottom of the reduction furnace. The first electrode 113 and the second electrode 114 are connected to a power source 115 (such as a DC or AC power source) for generating an electric arc that heats the carbothermal reduction process. The tantalum melt formed in the reduction furnace 114 is caused to flow out to the bucket 119 via the discharge zone of the reduction furnace 114, which has been preheated by the bucket preheating device 135. During the outflow, an inert gas such as argon may be bubbled through the bucket to agitate the helium melt therein. The material can be continuously added to the reduction furnace 111.

該還原爐111隨意地具有分離體，其中該上部分可與該下部分獨立地旋轉。該填滿的澆斗119被移至用於氯精製之配置，於氯精製期間，將氯氣隨意地連同惰性氣體(諸如氬)鼓泡通過該澆斗119中之液態矽，以與雜質(諸如鋁或鈣)反應以形成氯化物鹽，例如AlCl₃及CaCl₂。當該氯化物隨後與空氣接觸時，形成對應之氧化物。又，再次形成氯氣。然後該等氣體係在氣體清潔系統121中被純化，且較佳係送至該用於煙道氣過濾及粉塵處理裝置117的煙囪118。用於氯精製之配置較佳包含該液態矽之加熱構件120，諸如感應加熱。此係確使於此程序期間該矽維持液態。 The reduction furnace 111 optionally has a separate body, wherein the upper portion is rotatable independently of the lower portion. The filled bucket 119 is moved to a configuration for chlorine refining, during which the chlorine gas is optionally bubbled through an inert gas (such as argon) through the liquid helium in the bucket 119 to interfere with impurities (such as Aluminum or calcium) reacts to form chloride salts such as AlCl ₃ and CaCl ₂ . When the chloride is subsequently contacted with air, a corresponding oxide is formed. Also, chlorine gas is formed again. The gas systems are then purified in gas cleaning system 121 and preferably sent to chimney 118 for flue gas filtration and dust treatment unit 117. The configuration for chlorine refining preferably comprises the liquid crucible heating member 120, such as induction heating. This is to ensure that the crucible remains liquid during this procedure.

然後隨意地在過濾之後，將該經精製的矽熔體添加至在填充位置中用於定向凝固的裝置123上之較佳經預熱之坩堝/模122。該經精製矽亦可在添加至經預熱坩堝122之 前於感應爐或保溫爐中貯存一段時間。該裝置包含具有加熱元件125之爐124。當坩堝/模122已填滿時，該用於定向凝固之裝置係放置在其處理位置126，在10該位置126中該坩堝/模122係放置於該爐124中。在處理期間，該坩堝/模122係從下方冷卻以產生從底部向上凝固，其造成雜質集中在所形成之固態矽錠的頂層中。然後在該坩堝/模移出步驟127中將該坩堝/模122從該錠移出。此通常涉及使該坩堝/模122破裂以使該錠脫離。然後在錠裁切步驟128中裁切該錠移除其側邊及底部的最外層以及含雜質頂層。然後在該錠運送給消費者之前，可對該錠進行蝕刻及清洗(129)、裝填(130)及貯存(131)之步驟，此可使該錠再結晶，然後將其切成用於製造太陽能電池板的晶圓。 The refined ruthenium melt is then optionally added, after filtration, to the preferred preheated ruthenium/die 122 on the means 123 for directional solidification in the fill position. The refined crucible may also be added to the preheated crucible 122 Stored in the induction furnace or holding furnace for a period of time. The apparatus includes a furnace 124 having a heating element 125. When the die 122 is filled, the means for directional solidification is placed at its processing position 126 where it is placed in the furnace 124. During processing, the die 122 is cooled from below to create solidification from the bottom, which causes impurities to concentrate in the top layer of the solid ingot formed. The die/die 122 is then removed from the ingot in the die/die removal step 127. This typically involves breaking the jaw/die 122 to disengage the ingot. The ingot is then cut in an ingot cutting step 128 to remove the outermost layer of its sides and bottom and the top layer containing impurities. The ingot may then be etched and cleaned (129), filled (130), and stored (131) before the ingot is shipped to the consumer, which may recrystallize the ingot and then cut it into a manufacturing process. Solar panel wafers.

該錠裁切步驟128中所移除之所有及部分側邊及底部層係再循環至該程序，較佳係於研磨、噴砂及/或壓碎步驟132之後再循環至該用於秤重及混合之配置109。將來自該錠裁切步驟128之頂層丟棄以防止雜質累積在該系統100中。該研磨、噴砂及/或壓碎步驟132亦產生許多廢棄物。 All and a portion of the side and bottom layers removed in the ingot cutting step 128 are recycled to the process, preferably after the grinding, sand blasting and/or crushing step 132, to the weighing and Mixed configuration 109. The top layer from the ingot cutting step 128 is discarded to prevent accumulation of impurities in the system 100. The grinding, sandblasting and/or crushing step 132 also produces a plurality of waste.

用於進行石英之碳熱還原的還原爐之範例具體實例係於下文參考圖2加以描述。還原爐200具有開放式頂部，經由該開放式頂部添加起始材料(製備之二氧化矽(尤其是矽石)及/或石英、碳源(尤其是碳化矽及/或碳水化合物及隨意的再循環之矽金屬)。該還原爐200包含第二/中間襯裡201，較佳係由添加作為起始材料之相同類型的所製備 石英構成。該還原爐200尤其是包含由所主張之組成物構成的內部襯裡202，該組成物為例如高純度碳化矽(與添加起始材料者相同)、高純度矽(尤其是與圖1之系統所製造者相同)及高純度合成樹脂的混合物，在該還原爐200之底部將石墨或碳搗製糊之塊203配置在該中間襯裡201及該內部襯裡202之間。尤其是，該內部襯裡係由所主張之組成物構成。該還原爐200係藉由外殼204保持在一起，該外殼204可由鋼構成。隨意地，該爐可建構成具有可與下部分獨立地旋轉的上環部分之分離體。該10外殼204通常配置在該中間襯裡201外部。此外，可將絕緣層207(諸如絕緣織物)配置在該外殼204及該中間襯裡201之間。此種絕緣層207通常為薄層。較佳地，其具有小於10 mm，諸如約5 mm之厚度。若該絕緣層207太厚，則經由該還原爐底部及/或側邊傳送的熱變得太低而無法有效率冷卻該中間襯裡。將絕緣層207配置在該中間襯裡201及該外殼204之間的目的之一係促進該等襯裡201、202相對於該外殼的移動。此等移動通常係由溫度變化期間該襯裡材料的膨脹或收縮所導致。 An exemplary embodiment of a reduction furnace for performing carbothermal reduction of quartz is described below with reference to FIG. The reduction furnace 200 has an open top through which the starting material (prepared cerium oxide (especially vermiculite) and/or quartz, carbon source (especially strontium carbide and/or carbohydrates and optionally arbitrarily) is added via the open top. Circulating base metal. The reduction furnace 200 comprises a second/intermediate liner 201, preferably prepared by adding the same type as the starting material. Quartz composition. The reduction furnace 200 comprises, inter alia, an inner lining 202 composed of the claimed composition, such as high purity niobium carbide (same as the addition of starting materials), high purity niobium (especially with the system of Figure 1) A mixture of high-purity synthetic resin is disposed between the intermediate liner 201 and the inner liner 202 at the bottom of the reduction furnace 200 with a mixture of graphite or carbon crucible paste. In particular, the inner lining is composed of the claimed composition. The reduction furnace 200 is held together by a casing 204 which may be constructed of steel. Optionally, the furnace can be constructed as a separate body having an upper ring portion that is rotatable independently of the lower portion. The 10 outer casing 204 is typically disposed outside of the intermediate liner 201. Further, an insulating layer 207, such as an insulating fabric, may be disposed between the outer casing 204 and the intermediate liner 201. Such an insulating layer 207 is typically a thin layer. Preferably, it has a thickness of less than 10 mm, such as about 5 mm. If the insulating layer 207 is too thick, the heat transferred through the bottom and/or sides of the reduction furnace becomes too low to efficiently cool the intermediate liner. One of the purposes of disposing the insulating layer 207 between the intermediate liner 201 and the outer casing 204 is to facilitate movement of the liners 201, 202 relative to the outer casing. Such movements are typically caused by expansion or contraction of the lining material during temperature changes.

由本發明之含矽材料所構成的第一電極205或一組第一電極延伸至該還原爐200內部上方。此外，第二電極208從底部延伸通過外殼204及中間襯裡201且進入由本發明之含矽材料所構成的塊203。該等電極205、206可連接至電源(未圖示)。此外，電線圈208可提供在爐體周圍以用於旋轉該爐內部之電極所產生的電弧。該還原爐200 另外包含在其底部的放液區(未圖示)。該放液區包含通道/流道，於該還原爐200中形成的矽可經由該通道/流道流出該還原爐200。該放液區內部(包括該通道)係由內部襯裡202所構成。因此，該內部襯裡202係唯一接觸所形成之矽的材料。 The first electrode 205 or a set of first electrodes composed of the cerium-containing material of the present invention extends above the inside of the reduction furnace 200. In addition, the second electrode 208 extends from the bottom through the outer casing 204 and the intermediate liner 201 and into the block 203 comprised of the cerium-containing material of the present invention. The electrodes 205, 206 can be connected to a power source (not shown). Additionally, electrical coil 208 can be provided around the furnace for rotating the arc generated by the electrodes inside the furnace. The reduction furnace 200 Also included is a liquid discharge zone (not shown) at the bottom. The liquid discharge zone includes a passage/flow passage through which the crucible formed in the reduction furnace 200 can flow out of the reduction furnace 200. The interior of the drainage zone, including the channel, is comprised of an inner liner 202. Thus, the inner liner 202 is the only material that contacts the formed crucible.

該還原爐200可具有上部分，該上部分可與該下部分獨立地繞該第一電極旋轉。圖2之還原爐的範例工業設定茲參考圖3加以描述。在設定300中，將具有放液配置/放液區302之還原爐301配置成使在該還原爐301底部的液態矽可經由該放液區302的通道倒入放置在該還原爐301旁的澆斗303。 The reduction furnace 200 can have an upper portion that can rotate about the first electrode independently of the lower portion. An example industrial setting of the reduction furnace of Figure 2 is described with reference to Figure 3. In setting 300, the reduction furnace 301 having the liquid discharge configuration/drainage zone 302 is configured such that liquid helium at the bottom of the reduction furnace 301 can be poured into the reduction furnace 301 via the passage of the liquid discharge zone 302. Bucket 303.

操作員可使用放液設備304以控制放液程序。第一電極305可附接至在還原爐301上方的頂部(隨意地在建築構造內)，以使得可在上下位置之間移動。第二電極306係如圖2般配置。用於收集在該程序中所形成之氣體的防煙頭罩307亦附接於該頂部且配置在該還原爐301上方。還原爐301可分成上部分及包括爐301之底部的下部分，且該上部分可以可旋轉的方式附接於該下部分。 The operator can use the tapping device 304 to control the dispensing procedure. The first electrode 305 can be attached to the top above the reduction furnace 301 (optionally within the building construction) such that it can be moved between upper and lower positions. The second electrode 306 is configured as shown in FIG. A smoke mask 307 for collecting the gas formed in the program is also attached to the top and disposed above the reduction furnace 301. The reduction furnace 301 can be divided into an upper portion and a lower portion including the bottom of the furnace 301, and the upper portion can be rotatably attached to the lower portion.

實施例1、2： Examples 1, 2:

壓實測量：在一壓機中以1 kg壓模壓縮含矽材料之圓柱(直徑50 mm，高50 mm)。因壓模之重量所致之「無施力」壓縮(體積縮減)與預壓縮相關。之後，測量力/衝程圖(衝壓方式的力-位移)直到強度一致為止。該含矽材料在 該維度具有2.4倍之壓縮比，此與30 mm之衝壓方式有關。 Compaction measurement: A cylinder containing a crucible material (50 mm in diameter and 50 mm in height) was compressed in a press with a 1 kg stamper. The "no force" compression (volume reduction) due to the weight of the stamp is related to pre-compression. After that, the force/stroke diagram (force-displacement of the stamping method) is measured until the intensity is consistent. The bismuth-containing material is This dimension has a compression ratio of 2.4, which is related to the 30 mm stamping method.

實例電極1： Example electrode 1:

從具有下列組成物之含矽材料形成且製造未淬火電極： An unhardened electrode is formed and fabricated from a niobium containing material having the following composition:

含矽材料： Antimony material:

90%(w/w)之碳化矽糊；7.5%(w/w)之矽產物(sunsil®，純度>99.9999%，包括鐵之金屬<5 ppma)，原粒子為100至200 nm，2-5 μm二次粒子，孔隙度至高達97%)；2.5%(w/w)酚醛清漆。 90% (w/w) carbonized paste; 7.5% (w/w) of tantalum product (sunsil®, purity >99.9999%, including iron metal <5 ppma), primary particles 100 to 200 nm, 2- 5 μm secondary particles, porosity up to 97%); 2.5% (w/w) novolac.

將該材料混合且形成圓柱形，並根據下述製程參數來固化、回火及加熱。該材料亦用於形成還原爐體之內部襯裡。 The material was mixed and formed into a cylindrical shape and cured, tempered and heated according to the following process parameters. This material is also used to form the internal lining of the reduction furnace body.

分析方法：IPC-MS Analytical method: IPC-MS

用於搗製糊之SiC部分：For the SiC part of the paste:

用於固化、回火及加熱之方法：製程步驟(i)及(ii)尤其關鍵，且使用降低之加熱速率。步驟(iii)不是極為關鍵，但選擇稍微降低之速度。防止於該程序期間該含矽可擠出材料糊(尤其是團狀物)氧化。在該爐中填滿氬，以使該氛圍為還原性。關閉該爐且與氧隔絕。因此，視需要，該爐基本上係密封。多少氣密之頭罩及惰性氣體入口係接 近該底部。 Methods for curing, tempering and heating: Process steps (i) and (ii) are especially critical and use reduced heating rates. Step (iii) is not extremely critical, but choose a slightly lower speed. The oxidation of the ruthenium-containing extrudable material paste (especially agglomerates) during the process is prevented. The furnace was filled with argon to make the atmosphere reductive. The furnace is turned off and isolated from oxygen. Therefore, the furnace is substantially sealed as needed. How many airtight hoods and inert gas inlets are connected Near the bottom.

從900-1000℃(度)且至高達1400℃，係從氬切換成氮，以獲得介於所添加之Si金屬及氮之間的牢固結合之氮化物連接(Si₃N₄)。 From 900-1000 ° C (degrees) and up to 1400 ° C, switching from argon to nitrogen to obtain a strong bond between the added Si metal and nitrogen nitride bond (Si ₃ N ₄ ).

在爐電極之第二製造方法中，在整體加熱程序期間係使用氮。 In the second method of manufacturing the furnace electrode, nitrogen is used during the overall heating process.

實例電極2-含矽材料： Example electrode 2 - containing bismuth material:

90%(w/w)之碳化矽糊；5%(w/w)之矽產物(sunsil®，純度>99.9999%，包括鐵之金屬<5 ppma)，原粒子為100至200 nm，2-5 μm二次粒子，孔隙度至高達97%)；5%(w/w)酚醛清漆。糊之組成係根據表1及2(見前文)。 90% (w/w) carbonized paste; 5% (w/w) of tantalum product (sunsil®, purity >99.9999%, including iron metal <5 ppma), primary particles 100 to 200 nm, 2- 5 μm secondary particles, porosity up to 97%); 5% (w/w) novolac. The composition of the paste is based on Tables 1 and 2 (see above).

將該材料混合且形成圓柱形，並根據下述製程參數來固化、回火及加熱。 The material was mixed and formed into a cylindrical shape and cured, tempered and heated according to the following process parameters.

100‧‧‧系統 100‧‧‧ system

101‧‧‧天然石英 101‧‧‧Natural quartz

102‧‧‧處理設備 102‧‧‧Processing equipment

103‧‧‧一些石英 103‧‧‧some quartz

104‧‧‧碳黑 104‧‧‧Carbon black

105‧‧‧碳化矽製造設備 105‧‧‧Carbide manufacturing equipment

106‧‧‧經處理石英 106‧‧‧Processed Quartz

107‧‧‧再循環矽金屬 107‧‧‧Recycled base metal

108‧‧‧碳化矽 108‧‧‧Carbide

109‧‧‧用於秤重及混合之配置 109‧‧‧Configuration for weighing and mixing

110‧‧‧加料設備 110‧‧‧Feeding equipment

111/200/301‧‧‧還原爐 111/200/301‧‧‧Reduction furnace

112‧‧‧防煙頭罩 112‧‧‧ smoke hood

113/205/305‧‧‧第一電極 113/205/305‧‧‧ first electrode

114/206/306‧‧‧第二電極 114/206/306‧‧‧second electrode

115‧‧‧電源 115‧‧‧Power supply

116‧‧‧導管 116‧‧‧ catheter

117‧‧‧煙道氣過濾及粉塵處理裝置 117‧‧‧ Flue gas filtration and dust treatment device

118‧‧‧煙囪 118‧‧‧ chimney

119/303‧‧‧澆斗 119/303‧‧ ‧ bucket

120‧‧‧加熱構件 120‧‧‧heating components

121‧‧‧氣體清潔系統 121‧‧‧Gas cleaning system

122‧‧‧坩堝/模 122‧‧‧坩埚/模

123‧‧‧用於定向凝固的裝置 123‧‧‧Devices for directional solidification

124‧‧‧爐 124‧‧‧ furnace

125‧‧‧加熱元件 125‧‧‧ heating element

126‧‧‧處理位置 126‧‧‧Processing location

127‧‧‧坩堝/模移出步驟 127‧‧‧坩埚/Mold removal steps

128‧‧‧錠裁切步驟 128‧‧‧Ingot cutting steps

129‧‧‧蝕刻及清洗 129‧‧‧etching and cleaning

130‧‧‧裝填 130‧‧‧Loading

131‧‧‧貯存 131‧‧‧Storage

132‧‧‧研磨、噴砂及/或壓碎 132‧‧‧ grinding, sandblasting and/or crushing

135‧‧‧澆斗預熱裝置 135‧‧‧Powder preheating device

201‧‧‧第二/中間襯裡 201‧‧‧Second/intermediate lining

202‧‧‧內部襯裡 202‧‧‧Internal lining

203‧‧‧塊 203‧‧‧

204‧‧‧外殼 204‧‧‧ Shell

207‧‧‧絕緣層 207‧‧‧Insulation

208‧‧‧電線圈 208‧‧‧Electric coil

300‧‧‧設定 300‧‧‧Setting

302‧‧‧放液配置/放液區 302‧‧‧Liquid Disposition/Drainage Zone

304‧‧‧放液設備 304‧‧‧Draining equipment

307‧‧‧防煙頭罩 307‧‧‧ smoke hood

圖1顯示用於製造太陽能等級矽的整體系統之具體實例，其具有本發明電極113(底部電極未顯示於圖中)。 Figure 1 shows a specific example of an overall system for fabricating a solar grade crucible having an electrode 113 of the invention (bottom electrode not shown in the Figures).

圖2顯示用於進行將製備之石英材料碳熱還原成矽的還原爐體，其具有本發明之電極205(底部電極未顯示於圖 中)。 2 shows a reduction furnace body for performing a carbon reduction of a prepared quartz material to a crucible having the electrode 205 of the present invention (the bottom electrode is not shown in the drawing) in).

圖3顯示還原爐體之工業設定，其具有電極305。 Figure 3 shows an industrial setting of a reduction furnace body having an electrode 305.

圖4顯示矽粉末：原粒子之TEM影像。 Figure 4 shows 矽 powder: TEM image of the original particles.

圖5顯示矽粉末：二次粒子之REM影像。 Figure 5 shows the M powder: REM image of secondary particles.

圖6顯示矽粉末：結晶部分之TEM影像。 Figure 6 shows a TEM image of the enamel powder: crystalline portion.

300‧‧‧設定 300‧‧‧Setting

301‧‧‧還原爐 301‧‧‧Reduction furnace

302‧‧‧放液配置/放液區 302‧‧‧Liquid Disposition/Drainage Zone

303‧‧‧澆斗 303‧‧‧Pour bucket

304‧‧‧放液設備 304‧‧‧Draining equipment

305‧‧‧第一電極 305‧‧‧First electrode

306‧‧‧第二電極 306‧‧‧second electrode

307‧‧‧防煙頭罩 307‧‧‧ smoke hood

Claims (32)

一種用於藉由碳熱還原來製造矽之設備的組件，其特徵在於該組件包含：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(iii)0.1-5%(w/w)之黏結劑反應產物及/或黏結劑，如樹脂，例如合成樹脂，且其中此組成物的總合為100%(w/w)。 An assembly for apparatus for making tantalum by carbothermal reduction, characterized in that the assembly comprises: (i) 80-95% (w/w) of boron containing 1.5 ppm (w/w) or less and 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) Or less phosphorus bismuth product; and (iii) 0.1-5% (w/w) of a binder reaction product and/or a binder, such as a resin, such as a synthetic resin, and wherein the total composition of the composition is 100% (w/w). 如申請專利範圍第1項之用於藉由碳熱還原來製造矽之設備的組件，其中該組件係選自還原爐體之內部襯裡；SiC爐之內部襯裡；加熱或乾燥烘箱之內部襯裡；製粒、製錠、壓塊設備之內部襯裡；擠出器、電極組件、電極、放液通道、供給通道、放液設備之組件、澆斗、坩堝之內部襯裡；保溫爐之內部襯裡；定向凝固爐之內部襯裡；與石英、碳化矽、矽產物或包含石英、碳化矽、矽產物中任一者之調配物接觸的裝置之襯裡；供給通道之內部襯裡及供給管之內部襯裡。 An assembly for apparatus for producing crucibles by carbothermal reduction according to claim 1 wherein the component is selected from the interior lining of a reduction furnace body; the inner lining of the SiC furnace; the inner lining of the heating or drying oven; Internal lining of granulation, ingot making and briquetting equipment; extruder, electrode assembly, electrode, draining channel, supply channel, assembly of liquid discharge equipment, internal lining of bucket, crucible; internal lining of holding furnace; orientation The inner lining of the solidification furnace; the lining of the device in contact with quartz, tantalum carbide, niobium product or a formulation comprising any of quartz, tantalum carbide, niobium products; the inner lining of the supply passage and the inner lining of the supply tube. 如申請專利範圍第1或2項之組件，其中該碳化矽產物或矽產物中之所有其他金屬(排除矽)的總和分別少於100 ppm(w/w)，其中尤其是該等其他金屬係選自Ag、Al、As、Au、Ba、Be、Bi、Ca、Cd、Ce、Co、Cr、Cs、Cu、Dy、Er、Eu、Fe、Ga、Gd、Ge、Hf、Hg、Ho、In、 Ir、K、La、Li、Lu、Mg、Mn、Mo、Na、Nb、No、Os、Pb、Pd、Pr、Pt、Rb、Re、Rh、Ru、Sb、Sc、Se、Sm、Sn、Ta、Tb、Te、Th、Ti、Tl、Tm、U、W、Y、Yb、Zn、Zr，或其中該碳化矽產物及該矽產物中之該等其他金屬的總和少於100 ppm(w/w)，尤其是少於80 ppm(w/w)。 The component of claim 1 or 2, wherein the sum of all other metals in the niobium carbide product or niobium product (excluding niobium) is less than 100 ppm (w/w), respectively, especially among other metal systems Selected from Ag, Al, As, Au, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, In, Ir, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, No, Os, Pb, Pd, Pr, Pt, Rb, Re, Rh, Ru, Sb, Sc, Se, Sm, Sn, Ta, Tb, Te, Th, Ti, Tl, Tm, U, W, Y, Yb, Zn, Zr, or wherein the sum of the niobium carbide product and the other metals in the niobium product is less than 100 ppm (w /w), especially less than 80 ppm (w/w). 如申請專利範圍第3項之組件，其中該碳化矽產物及該矽產物中選自下列的該等其他金屬係等於或少於：a.鋁(Al)30 ppm(w/w)或為25至0.0001 ppt(w/w)，尤其是22 ppm(w/w)至0.0001 ppt(w/w)，及b.硼(B)1.0 ppm(w/w)至0.0001 ppt(w/w)，尤其是0.5 ppm(w/w)至0.0001 ppt(w/w)，較佳為0.4 ppm(w/w)至0.0001 ppt(w/w)，或特佳為0.35 ppm(w/w)至10 ppb(w/w)；及c.鈣(Ca)20 ppm(w/w)，尤其是15至0.0001 ppt(w/w)，較佳為10 ppm(w/w)至0.0001 ppt(w/w)；及隨意的d.鎵(Ga)1 ppm，尤其是0.5 ppm至0.0001 ppt(w/w)，較佳為0.1 ppm(w/w)至0.0001 ppt(w/w)，尤佳為1 ppb(w/w)至0.0001 ppt(w/w)，e.鎳(Ni)10 ppm(w/w)，尤其是5 ppm(w/w)至0.0001 ppt(w/w)，較佳為3.5 ppm及0.0001 ppt(w/w)；f.磷(P)3 ppm(w/w)至0.0001 ppt(w/w)，尤其是2 ppm(w/w)至0.0001 ppt(w/w)，較佳為1 ppm(w/w)至 0.0001 ppt(w/w)，及g.鈦(Ti)2 ppm(w/w)，尤其是1.7 ppm(w/w)至0.0001 ppt，較佳為1.5至0.0001 ppt(w/w)；及h.鋅(Zn)30 ppm(w/w)，尤其是25 ppm(w/w)至0.0001 ppt(w/w)，較佳為10 ppm至0.0001 ppt(w/w)。 The component of claim 3, wherein the niobium carbide product and the other metal of the niobium product selected from the group consisting of: a. aluminum (Al) 30 ppm (w/w) or 25 Up to 0.0001 ppt (w/w), especially 22 ppm (w/w) to 0.0001 ppt (w/w), and b. boron (B) 1.0 ppm (w/w) to 0.0001 ppt (w/w), Especially 0.5 ppm (w/w) to 0.0001 ppt (w/w), preferably 0.4 ppm (w/w) to 0.0001 ppt (w/w), or particularly preferably 0.35 ppm (w/w) to 10 Ppb(w/w); and c. calcium (Ca) 20 ppm (w/w), especially 15 to 0.0001 ppt (w/w), preferably 10 ppm (w/w) to 0.0001 ppt (w/ w); and random d. gallium (Ga) 1 ppm, especially 0.5 ppm to 0.0001 ppt (w/w), preferably 0.1 ppm (w/w) to 0.0001 ppt (w/w), especially preferably 1 ppb (w/w) to 0.0001 ppt (w/w), e. nickel (Ni) 10 ppm (w/w), especially 5 ppm (w/w) to 0.0001 ppt (w/w), preferably 3.5 ppm and 0.0001 ppt (w/w); f. phosphorus (P) 3 ppm (w/w) to 0.0001 ppt (w/w), especially 2 ppm (w/w) to 0.0001 ppt (w/w) ), preferably 1 ppm (w/w) to 0.0001 ppt(w/w), and g. titanium (Ti) 2 ppm (w/w), especially 1.7 ppm (w/w) to 0.0001 ppt, preferably 1.5 to 0.0001 ppt (w/w); h. Zinc (Zn) 30 ppm (w/w), especially 25 ppm (w/w) to 0.0001 ppt (w/w), preferably 10 ppm to 0.0001 ppt (w/w). 如申請專利範圍第1或2項之組件，其中該組件為未淬火體且包含選自以下之組成物：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；其中該矽產物為矽，及(iii)0.1-5%(w/w)之黏結劑，諸如樹脂、碳水化合物，例如合成樹脂、酚-甲醛樹脂及/或醣；且其中此組成物的總合為100%(w/w)。 The component of claim 1 or 2, wherein the component is an unquenched body and comprises a composition selected from the group consisting of: (i) 80-95% (w/w) containing 1.5 ppm (w/w) or Less boron and 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 a palladium product of ppm (w/w) or less; wherein the antimony product is antimony, and (iii) 0.1 to 5% (w/w) of a binder such as a resin, a carbohydrate, such as a synthetic resin, a phenol - formaldehyde resin and / or sugar; and wherein the total composition of this composition is 100% (w / w). 如申請專利範圍第1或2項之組件，其中該組件為經回火體，其包含選自以下之組成物：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；其中該矽產物包含氮化矽及隨意的矽，及(iii)0至5(w/w)之黏結劑反應產物，諸如樹脂、碳水化合物，例如合成樹脂及/或醣，且其中此組成物的總 The component of claim 1 or 2, wherein the component is a tempered body comprising a composition selected from the group consisting of: (i) 80-95% (w/w) containing 1.5 ppm (w/w) ) or less boron and 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) or less of boron And a cerium product of 3.0 ppm (w/w) or less of phosphorus; wherein the cerium product comprises cerium nitride and optionally cerium, and (iii) 0 to 5 (w/w) of a binder reaction product such as a resin , carbohydrates, such as synthetic resins and/or sugars, and the total of this composition 合為100%(w/w)。 一種用於藉由碳熱還原製造液態矽之還原爐體，該爐體包含內部襯裡，其特徵在於該內部襯裡包含：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(ii)0.1-5%(w/w)之黏結劑反應產物及/或黏結劑，如樹脂，例如合成樹脂；且尤其是其中此組成物的總合為100%(w/w)。 The combination is 100% (w/w). A reduction furnace for producing liquid helium by carbothermal reduction, the furnace body comprising an inner liner, characterized in that the inner liner comprises: (i) 80-95% (w/w) containing 1.5 ppm (w/ w) or less boron and 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) or less Boron and 3.0 ppm (w/w) or less of phosphorus bismuth product; and (ii) 0.1-5% (w/w) of binder reaction product and/or binder, such as a resin, such as a synthetic resin; In particular, the sum of the compositions therein is 100% (w/w). 如申請專利範圍第7項之還原爐體，其中該碳化矽產物及該矽產物各含有300 ppm(w/w)或更少之Al。 The reduction furnace body of claim 7, wherein the niobium carbide product and the niobium product each contain 300 ppm (w/w) or less of Al. 如申請專利範圍第7或8項之還原爐體，其中該碳化矽產物及該矽產物中所有金屬的總和分別少於500 ppm。 The reduction furnace body of claim 7 or 8, wherein the total amount of the niobium carbide product and all the metals in the niobium product is less than 500 ppm. 如申請專利範圍第7項之還原爐體，其包含由與該內部襯裡材料不同之材料所構成的第二襯裡，該第二襯裡係配置成與該內部襯裡之外表面接觸。 A reduction furnace body according to clause 7 of the patent application, comprising a second lining composed of a material different from the inner lining material, the second lining being configured to be in contact with an outer surface of the inner lining. 如申請專利範圍第10項之還原爐體，其中該第二襯裡之材料為矽石或矽石搗製糊。 The reducing furnace body of claim 10, wherein the material of the second lining is made of vermiculite or vermiculite. 如申請專利範圍第10項之還原爐體，其中將一層石墨或碳搗製糊配置在該爐體底部之內部襯裡及第二襯裡之間。 The reduction furnace body of claim 10, wherein a layer of graphite or carbon crucible paste is disposed between the inner lining of the bottom of the furnace body and the second lining. 如申請專利範圍第7項之還原爐體，其中該黏結 劑為選自合成酚-甲醛樹脂之樹脂。 Such as the reduction furnace body of claim 7 of the patent scope, wherein the bonding The agent is a resin selected from the group consisting of synthetic phenol-formaldehyde resins. 如申請專利範圍第7項之還原爐體，其中在爐體底部提供介於爐體內部與外部之間的可關閉之通道以供液態矽放液，且其中該通道的內壁係由該內部襯裡所構成。 The reduction furnace body of claim 7, wherein a closable passage between the inside and the outside of the furnace body is provided at the bottom of the furnace body for liquid helium discharge, and wherein the inner wall of the passage is from the interior The lining is composed. 如申請專利範圍第7項之還原爐體，其被分成上、下部分，其中該上部分係以可旋轉的方式附接於該下部分。 The reduction furnace body of claim 7, which is divided into upper and lower portions, wherein the upper portion is rotatably attached to the lower portion. 一種電極組件或電極，其特徵在於該電極之至少一組件包含具有選自以下之組成物的含矽材料：(i)80至95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5至20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(iii)0至5(w/w)之黏結劑反應產物或黏結劑，如樹脂，例如合成樹脂；且其中此組成物的總合為100%(w/w)。 An electrode assembly or electrode, characterized in that at least one component of the electrode comprises a cerium-containing material having a composition selected from the group consisting of: (i) 80 to 95% (w/w) containing 1.5 ppm (w/w) or Less boron and 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5 to 20% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 a palladium product of ppm (w/w) or less; and (iii) a binder reaction product or a binder of 0 to 5 (w/w), such as a resin, such as a synthetic resin; and wherein the total of the composition The combination is 100% (w/w). 如申請專利範圍第16項之電極，其中該電極為未淬火電極、爐電極，尤其是用於還原爐之爐電極，較佳為用於製造液態矽之還原爐的爐電極，更佳為用於藉由碳熱還原製造液態矽之還原爐的爐電極、爐底電極或至少該未淬火電極之組件。 The electrode of claim 16, wherein the electrode is an unquenched electrode, a furnace electrode, especially a furnace electrode for a reduction furnace, preferably a furnace electrode for producing a reduction furnace of liquid helium, preferably used A furnace electrode, a furnace bottom electrode or at least an assembly of at least the unquenched electrode of a reduction furnace for producing liquid helium by carbothermal reduction. 如申請專利範圍第2項之組件，其為電極或電極組件且其包括含有等於或少於1.5 ppm(w/w)之銀，尤其是少於1.0 ppm(w/w)之硼(B)，較佳為少於0.5 ppm (w/w)，更佳為少於0.2 ppm(w/w)及/或少於2.0 ppm(w/w)之磷(P)，尤其是等於或少於1.0 ppm(w/w)之磷，及隨意的等於或少於5 ppm(w/w)之硫(S)，尤其是少於4.5 ppm(w/w)之硫的含矽材料。 An assembly according to item 2 of the patent application, which is an electrode or an electrode assembly and which comprises boron containing equal to or less than 1.5 ppm (w/w), especially less than 1.0 ppm (w/w) of boron (B) , preferably less than 0.5 ppm (w/w), more preferably less than 0.2 ppm (w/w) and/or less than 2.0 ppm (w/w) of phosphorus (P), especially equal to or less than 1.0 ppm (w/w) Phosphorus, and optionally sulphur (S) equal to or less than 5 ppm (w/w), especially cerium containing less than 4.5 ppm (w/w) sulphur. 如申請專利範圍第2項之組件，其為澆斗或坩堝且其至少包括含有以下者之內部襯裡：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(iii)0.1-5%(w/w)之黏結劑反應產物及/或黏結劑，如樹脂，例如合成樹脂；且其中此組成物的總合為100%(w/w)，尤其是該澆斗另外包含加熱構件之配置，較佳之加熱構件為感應加熱構件。 An assembly, as in claim 2, which is a bucket or crucible and which includes at least an internal lining containing: (i) 80-95% (w/w) containing 1.5 ppm (w/w) or more Less boron and 3.0 ppm (w/w) or less of phosphorus tantalum product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 ppm a (w/w) or less phosphorus antimony product; and (iii) 0.1 to 5% (w/w) of a binder reaction product and/or a binder such as a resin such as a synthetic resin; and wherein the composition The sum total is 100% (w/w), and in particular the bucket additionally includes a configuration of heating members, preferably the heating member is an induction heating member. 一種用於藉由碳熱還原來製造矽之設備的組件的製造方法，其中形成包含以下者之未淬火組件且隨意地將它固化：(i)80-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-20%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(iii)0.1-5%(w/w)之黏結劑及/或黏結劑，如樹脂，例如合成樹脂；且其中此組成物的總合為100%(w/w)。 A method of manufacturing an assembly for a device for manufacturing tantalum by carbothermal reduction, wherein an unquenched component comprising: and optionally cured is formed: (i) 80-95% (w/w) containing 1.5 Pb (w/w) or less boron and 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5-20% (w/w) containing 1.5 ppm (w/w) Or less boron and a palladium product of 3.0 ppm (w/w) or less; and (iii) 0.1-5% (w/w) of a binder and/or a binder, such as a resin, such as a synthetic resin And wherein the total composition of this composition is 100% (w/w). 如申請專利範圍第20項之方法，其具有以下步 驟：(i)固化所形成之未淬火組件，及隨意地(ii)將該未淬火組件回火，及隨意地(iii)加熱該未淬火組件，其中步驟(ii)之溫度高於步驟(i)，且步驟(iii)之溫度高於步驟(ii)。 For example, the method of claim 20 has the following steps Step: (i) curing the unquenched component formed, and optionally (ii) tempering the unquenched component, and optionally (iii) heating the unquenched component, wherein the temperature of step (ii) is higher than the step ( i), and the temperature of step (iii) is higher than step (ii). 如申請專利範圍第20或21項之方法，其中該未淬火組件係選自還原爐體之內部襯裡；SiC爐之內部襯裡；加熱或乾燥烘箱之內部襯裡；製粒、製錠、壓塊設備之內部襯裡；擠出器、電極組件、電極、放液通道、供給通道、放液設備之組件、澆斗、坩堝之內部襯裡；保溫爐之內部襯裡；定向凝固爐之內部襯裡；與石英、碳化矽、矽產物或包含石英、碳化矽、矽產物中任一者之調配物接觸的裝置之襯裡；供給通道之內部襯裡及供給管之內部襯裡。 The method of claim 20 or 21, wherein the unquenched component is selected from the interior lining of the reduction furnace body; the internal lining of the SiC furnace; the internal lining of the heating or drying oven; the granulation, ingot making, and the briquetting equipment Inner lining; extruder, electrode assembly, electrode, draining channel, supply channel, assembly of liquid discharge equipment, internal lining of bucket, crucible; internal lining of holding furnace; internal lining of directional solidification furnace; Lining of the tantalum carbide, niobium product or device comprising the formulation of any of quartz, tantalum carbide, niobium products; the inner lining of the supply channel and the inner lining of the supply tube. 如申請專利範圍第20或21項之方法，其中該固化、回火及/或加熱係於如氬之惰性氣體之氛圍中進行。 The method of claim 20, wherein the curing, tempering and/or heating is carried out in an atmosphere such as an inert gas of argon. 如申請專利範圍第20或21項之方法，其中該固化、回火及/或加熱係在含氮氛圍中進行，尤其是該加熱步驟係在含氮氛圍中進行，較佳係在氮氛圍中進行，例如10至100體積%之N₂及100體積%之惰性氣體，尤其是氬。 The method of claim 20 or 21, wherein the curing, tempering and/or heating is carried out in a nitrogen-containing atmosphere, in particular the heating step is carried out in a nitrogen-containing atmosphere, preferably in a nitrogen atmosphere. For example, 10 to 100% by volume of N ₂ and 100% by volume of an inert gas, in particular argon, are carried out. 如申請專利範圍第20或21項之方法，其中該未淬火組件係由包含以下者之組成物所形成：(i)85-95%(w/w)之含有1.5 ppm(w/w)或更少之硼及 3.0 ppm(w/w)或更少之磷的碳化矽產物；(ii)5-15%(w/w)之含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物；及(iii)0.1-2%(w/w)之黏結劑，如樹脂，例如合成樹脂；且其中此組成物的總和為100%(w/w)。 The method of claim 20, wherein the unquenched component is formed from a composition comprising: (i) 85-95% (w/w) containing 1.5 ppm (w/w) or Less boron and 3.0 ppm (w/w) or less of phosphorus niobium carbide product; (ii) 5-15% (w/w) containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) Or less phosphorous ruthenium product; and (iii) 0.1-2% (w/w) of a binder such as a resin such as a synthetic resin; and wherein the sum of the compositions is 100% (w/w). 如申請專利範圍第20或21項之方法，其中(i)於固化步驟期間之溫度為0至300℃，尤其是50至300℃，較佳為100至250℃，尤佳為150至250℃，各±25℃，及隨意地(ii)於回火步驟期間之溫度為200至500℃，尤其是200至450℃，較佳為250至400℃，各±25℃，及隨意地(iii)於加熱步驟期間之溫度為350至1400℃，尤其是在數步驟中為400至600℃或為600℃至1400℃，或為600至900℃，及為900至1400℃。 The method of claim 20 or 21, wherein (i) the temperature during the curing step is from 0 to 300 ° C, especially from 50 to 300 ° C, preferably from 100 to 250 ° C, particularly preferably from 150 to 250 ° C. , each ±25 ° C, and optionally (ii) during the tempering step, the temperature is 200 to 500 ° C, especially 200 to 450 ° C, preferably 250 to 400 ° C, each ± 25 ° C, and optionally (iii The temperature during the heating step is 350 to 1400 ° C, especially 400 to 600 ° C or 600 ° C to 1400 ° C in several steps, or 600 to 900 ° C, and 900 to 1400 ° C. 如申請專利範圍第26項之方法，其中在步驟(i)、(ii)及/或(iii)中該溫度設定為+5℃/小時，尤其是+10℃/小時，或+15℃/小時。 The method of claim 26, wherein in step (i), (ii) and/or (iii) the temperature is set to +5 ° C / hour, especially + 10 ° C / hour, or + 15 ° C / hour. 如申請專利範圍第21項之方法，其中於(i)、(ii)及/或(iii)各步驟中之保持時間獨立地為10至250小時，尤其是每一步驟之保持時間為25至150小時，較佳為50至100小時，特別是步驟(i)及(ii)。 The method of claim 21, wherein the holding time in each of steps (i), (ii) and/or (iii) is independently 10 to 250 hours, in particular, the holding time of each step is 25 to 150 hours, preferably 50 to 100 hours, especially steps (i) and (ii). 一種用於藉由碳熱還原來製造液態矽之設備的組件，其係藉由如申請專利範圍第20至28項中任一項之方 法製得。 An assembly for an apparatus for producing liquid helium by carbothermal reduction, by the method of any one of claims 20 to 28 Made by law. 如申請專利範圍第29項之組件，其中該組件係選自還原爐體之內部襯裡；SiC爐之內部襯裡；加熱或乾燥烘箱之內部襯裡；製粒、製錠、壓塊設備之內部襯裡；擠出器、電極組件、電極、放液通道、供給通道、放液設備之組件、澆斗、坩堝之內部襯裡；保溫爐之內部襯裡；定向凝固爐之內部襯裡；與石英、碳化矽、矽產物或包含石英、碳化矽、矽產物中任一者之調配物接觸的裝置之襯裡；供給通道之內部襯裡及供給管之內部襯裡；選自電極股(electrode strand)、電極主體(electrode body)、螺紋接管、閉鎖銷(blocking pin)、夾片(clamping jaw)、其或電極中任一者之安裝座或未淬火體，諸如底部電極或包含至少兩個上述電極組分之電極裝配件。 The assembly of claim 29, wherein the component is selected from the interior lining of the reduction furnace; the internal lining of the SiC furnace; the internal lining of the heating or drying oven; the internal lining of the granulation, ingot, and briquetting equipment; Extruder, electrode assembly, electrode, draining channel, supply channel, assembly of liquid discharge equipment, internal lining of bucket, crucible; internal lining of holding furnace; internal lining of directional solidification furnace; and quartz, tantalum carbide, niobium a product or a liner comprising means for contacting a formulation of any one of quartz, tantalum carbide, niobium product; an inner liner of the supply passage and an inner liner of the supply tube; selected from the group consisting of an electrode strand and an electrode body , a nipple, a blocking pin, a clamping jaw, a mount or an unquenched body of either of the electrodes, such as a bottom electrode or an electrode assembly comprising at least two of the above electrode components. 一種用於藉由碳熱還原製造液態矽之設備的組件的用途，其係用於藉由碳熱還原製造含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物，該製造包含以下步驟：a)將選自含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷，尤其是0.50 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷的矽石及石英產物之二氧化矽產物及包括含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的碳化矽產物、碳水化合物及/或蔗糖之碳源添加至具有至少一個電極之還原爐；及b)加熱該混合物以形成該矽產物的熔體， 其中該還原爐及/或申請專利範圍第1至30項中任一項之組件包含選自以下者之組成物：(i)80-95%(w/w)之具有與步驟a)中所添加之碳化矽產物至少相同純度的碳化矽產物，(ii)5-20%(w/w)之矽產物，尤其是包含氮化矽及隨意的矽，其至少具有由步驟a)及b)所製造之矽產物的純度；及(iii)0-5%(w/w)之黏結劑反應產物，如樹脂或碳水化合物。 Use of an assembly for an apparatus for producing liquid helium by carbothermal reduction, which is used to produce boron containing 1.5 ppm (w/w) or less and 3.0 ppm (w/w) by carbothermal reduction or A less phosphorus ruthenium product, the manufacture comprising the steps of: a) being selected from the group consisting of 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus, especially 0.50 ppm. (w/w) or less of boron and 1.0 ppm (w/w) or less of phosphorus of vermiculite and quartz products of ceria products and including boron containing 1.5 ppm (w/w) or less a carbon source of 3.0 ppm (w/w) or less of phosphorus, a carbon source of carbohydrates and/or sucrose is added to a reduction furnace having at least one electrode; and b) the mixture is heated to form a melt of the bismuth product , Wherein the reduction furnace and/or the assembly of any one of claims 1 to 30 comprises a composition selected from the group consisting of: (i) 80-95% (w/w) having the same as in step a) The added niobium carbide product has at least the same purity of niobium carbide product, (ii) 5-20% (w/w) of the niobium product, especially comprising tantalum nitride and random niobium, which have at least step a) and b) The purity of the produced ruthenium product; and (iii) 0-5% (w/w) of the binder reaction product, such as a resin or a carbohydrate. 一種用於藉由碳熱還原製造含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷的矽產物之方法，其包括下列步驟：將含有0.50 ppm(w/w)或更少之硼及1.0 ppm(w/w)或更少之磷的石英產物及含有1.5 ppm(w/w)或更少之硼及3.0 ppm(w/w)或更少之磷之碳化矽產物添加至具有內部襯裡之還原爐；及b)加熱該混合物以形成該矽產物的熔體，其中該襯裡包含：80-95%(w/w)之具有與步驟a)中所添加之碳化矽產物至少相同純度的碳化矽產物；5-20%(w/w)之至少具有由該方法所製造之矽產物的純度之矽產物；及0.1-5%(w/w)之黏結劑或黏結劑反應產物，如樹脂。 A method for producing a ruthenium product containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or less of phosphorus by carbothermal reduction, comprising the steps of: 0.50 ppm Quartz product of (w/w) or less boron and 1.0 ppm (w/w) or less of phosphorus and containing 1.5 ppm (w/w) or less of boron and 3.0 ppm (w/w) or more a phosphorus-free niobium carbide product is added to the reduction furnace having an inner liner; and b) heating the mixture to form a melt of the niobium product, wherein the liner comprises: 80-95% (w/w) having the same step a a cerium carbide product added in at least the same purity of the cerium carbide product; 5-20% (w/w) of a cerium product having at least the purity of the cerium product produced by the method; and 0.1-5% (w/ w) a binder or binder reaction product, such as a resin.