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CN1022335C - container for hydrothermal synthesis - Google Patents

container for hydrothermal synthesis Download PDF

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Publication number
CN1022335C
CN1022335C CN90101411.7A CN90101411A CN1022335C CN 1022335 C CN1022335 C CN 1022335C CN 90101411 A CN90101411 A CN 90101411A CN 1022335 C CN1022335 C CN 1022335C
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container
buffer chamber
inner tubular
tubular
tubular container
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CN1053819A (en
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千叶康太郎
烟中基秀
河合政征
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Japan Steel Works Ltd
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Japan Steel Works Ltd
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Priority to DE4003377A priority patent/DE4003377C1/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • B01J3/046—Pressure-balanced vessels
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
    • B01J2219/0236—Metal based

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

一种水热合成用容器，所说容器包括：从外部加热的容器体；一放置在所说容器体中并于其间形成有一管状空隙的内管状容器，所说内管状容器有一由诸如银、金或铂一类贵金属制备的内表面和一于其上有第一小孔的盖；和盖于第一小孔上的缓冲室，此缓冲室有一由此盖所限定的壁和有其上带有第二小孔的另一壁。

A container for hydrothermal synthesis, said container comprising: a container body heated from the outside; an inner tubular container placed in said container body and forming a tubular space therebetween, said inner tubular container having an inner surface made of a precious metal such as silver, gold or platinum and a cover having a first small hole thereon; and a buffer chamber covering the first small hole, said buffer chamber having a wall defined by the cover and another wall having a second small hole thereon.

Description

本发明涉及用水热合成生产如人造水晶所用的容器。The present invention relates to the hydrothermal synthesis for the production of containers such as artificial crystals.

水热合成通常用容器示于图4，它一般由容器体21、盖22、夹紧件23、对流控制板24、加热器25和热电偶26组成。容器体21中的晶种A和原料B浸于加热器25加热的强碱溶液中。以水热合成人造水晶为倒，是在350-400℃的温度及1000～1500Kg/cm2的压力下使用此容器，所以此容器体21必须用强度高，韧性好，耐腐蚀的金属材料制造。The usual container for hydrothermal synthesis is shown in FIG. 4 , which generally consists of a container body 21 , a cover 22 , a clamping member 23 , a convection control plate 24 , a heater 25 and a thermocouple 26 . The seed crystal A and raw material B in the container body 21 are immersed in the strong alkali solution heated by the heater 25 . Taking hydrothermal synthetic artificial crystal as an example, the container is used at a temperature of 350-400°C and a pressure of 1000-1500Kg/cm 2 , so the container body 21 must be made of a metal material with high strength, good toughness, and corrosion resistance .

水热合成的许多制品用于电子设备和光学设备，日益要求薄而小型化。如果用水热合成生产小而薄的带状制品时，其产品质量降低的主要原因是由于夹杂有外夹物质。特别应预指出的主要问题是，容器体21的内表面被强碱溶液腐蚀产生称作“锥辉石”的铁化合物，产品含有Fe+离子杂质。业已采用了多种方法来解决此问题，其办法之一是隔离晶种A的表面，然而此方法也不尽令人满意，经保护的晶种表面阻碍水晶的生长，从而使产率降低。Many hydrothermally synthesized products are used in electronic and optical devices, and are increasingly required to be thin and miniaturized. If hydrothermal synthesis produces small and thin strip-shaped products, the main reason for the reduction in product quality is due to the inclusion of external substances. The main problem that should be pointed out in particular is that the inner surface of the container body 21 is corroded by the strong alkali solution to produce iron compounds called "conopyroxene", and the product contains Fe + ion impurities. Various methods have been used to solve this problem. One of the methods is to isolate the surface of the seed crystal A. However, this method is not satisfactory. The protected surface of the seed crystal hinders the growth of the crystal, thereby reducing the yield.

所采取的另一措施是，在容器体21的内表面上涂水银，金或铂一类贵金属或是在容器体21内放入一由这些贵金属制的内管状容器，从本质上讲这是阻止铁离子的产生，此第一种方法是在容器体21的内表面上涂复水银，金或铂一类贵金属，必须对此管状体进行液压膨胀或爆炸熔粘一类措施的以确保贵金属涂层和容器体21内表面之间粘结，但在制备此容器时，将会碰到相当大困难。而且，根据容器体21的结构，会发生不足矣需持封闭区板面的情况。在第二种方法中，即将如银，金或铂制的内管状容器放入容器体21内，这时必须使内管状容器内的压力等于外部的工作压力，从而不会使过高的外压作用到此内容器上。因此，必须保持内容器中的液体体积等于此容器外液体体积。鉴于上述原因，力图用以阻止Fe+离子产生的上述两种方法已适用的仅仅是小型的实验室容器。Another measure taken is to coat mercury on the inner surface of the container body 21, precious metals such as gold or platinum or put an inner tubular container made of these precious metals in the container body 21, which is essentially To prevent the generation of iron ions, the first method is to coat the inner surface of the container body 21 with precious metals such as mercury, gold or platinum. Measures such as hydraulic expansion or explosive fusion must be carried out on this tubular body to ensure that the precious metal Adhesion between the coating and the inner surface of the container body 21 will be achieved, but considerable difficulties will be encountered in the manufacture of this container. Moreover, depending on the structure of the container body 21, it may not be enough to hold the plate surface of the closed area. In the second method, the inner tubular container such as silver, gold or platinum is put into the container body 21. At this time, the pressure in the inner tubular container must be equal to the external working pressure, so as not to cause excessive external pressure. Pressure is applied to this inner container. Therefore, it is necessary to keep the volume of liquid in the inner container equal to the volume of liquid outside this container. For the above reasons, the above two methods in an attempt to prevent the generation of Fe + ions have been applicable only to small laboratory vessels.

鉴于上述，本发明的主要目的是提供一种大型的，适用于工业操作的水热合成用容器。根据本发明的第一个目的，本发明提供的水热合成用容器包括一个放于所说容器体中的管状容器，其间有一管状空隙，至少管状容器的内表面是由如银、金或铂一类贵金属制备的，此内管状容器的盖上带有一小孔，所说的合成用容器还包括一缓冲室，此缓冲室盖住所说的小孔，所说缓冲室的一个表面由所说的盖限定，在所说的缓冲室的另一壁面上也带有一小孔。In view of the above, the main purpose of the present invention is to provide a large container for hydrothermal synthesis suitable for industrial operation. According to the first object of the present invention, the hydrothermal synthesis container provided by the present invention comprises a tubular container placed in said container body, there is a tubular space therebetween, at least the inner surface of the tubular container is made of silver, gold or platinum A kind of precious metal preparation, the lid of this inner tubular container has a small hole, said synthesis container also includes a buffer chamber, this buffer chamber covers said small hole, one surface of said buffer chamber is covered by said The lid limit, also has an aperture on the other wall surface of said buffer chamber.

根据本发明的另一目的，在上述容器的缓冲室空间，管状空隙的有效空间和内管状容器的有效空间装有按特定比例的碱溶液，按规定，缓冲室和管状空隙中的碱溶液浓度要低于内管状容器中的碱溶液浓度。According to another object of the present invention, in the buffer chamber space of the above-mentioned container, the effective space of the tubular void and the effective space of the inner tubular container are equipped with an alkali solution in a specific ratio, and the concentration of the alkali solution in the buffer chamber and the tubular void is as specified. To be lower than the alkali solution concentration in the inner tubular container.

根据本发明的上述两个目的，容器体和内管状容器之间的所说管状空隙中填满导热性能好的透气 性材料。According to the above two purposes of the present invention, the said tubular space between the container body and the inner tubular container is filled with good heat-conducting air-permeable sexual material.

图1为根据本发明实例的水热合成用容器的半剖面图。Fig. 1 is a half-sectional view of a container for hydrothermal synthesis according to an example of the present invention.

图2是图1所示的容器的内管状容器的盖的主要部分和缓冲室的剖面图。Fig. 2 is a sectional view of the main part of the cover of the inner tubular container and the buffer chamber of the container shown in Fig. 1 .

图3是改进设计的内管状容器盖的主要部分和缓冲室的剖面图。Fig. 3 is a sectional view of the main part and the buffer chamber of the improved design of the inner tubular container cover.

图4是水热合成用现有公知容器的剖面图。Fig. 4 is a sectional view of a conventional known container for hydrothermal synthesis.

本发明的内管状容器装晶种和原料，从外部加热容器体以进行水热合成。至少内管状容器的内表面用贵金属制备，这样水热合成期间容器内便不会产生对晶种有害的铁离子。The inner tubular container of the present invention contains seed crystals and raw materials, and the container body is heated from the outside to carry out hydrothermal synthesis. At least the inner surface of the inner tubular container is made of noble metal so that no iron ions, which are harmful to the seeds, are generated in the container during hydrothermal synthesis.

容器体和内管状容器之间的管状空隙通过在它的盖和缓冲室的壁上设置的小孔与内管状容器的内部相通，这样内管状容器中的压力将与外部的压力相等从而保证适中的外压作用到内管状容器上。内管状容器将不会变形或损害。The tubular space between the container body and the inner tubular container communicates with the inside of the inner tubular container through small holes provided on its cover and the wall of the buffer chamber, so that the pressure in the inner tubular container will be equal to the external pressure to ensure moderate The external pressure acts on the inner tubular container. The inner tubular container will not be deformed or damaged.

如果缓冲室的空间，管状空隙的有效空间及内管状容器的有效空间装有特定比例的碱溶液。如果使缓冲室和管状空隙中的碱溶液浓度低于内管状容器中的碱溶液浓度，管状空隙中的压力基本上与内管状容器中的压力相等。压力的任何变化均将被内管状容器的盖上和缓室壁上的小孔所缓冲，从而恢复管状空隙和内管状容器压力间的平衡。If the space of the buffer chamber, the effective space of the tubular void and the effective space of the inner tubular container are filled with a certain proportion of alkali solution. If the concentration of the alkaline solution in the buffer chamber and the tubular space is lower than that in the inner tubular container, the pressure in the tubular space is substantially equal to the pressure in the inner tubular container. Any change in pressure will be buffered by the lid of the inner tubular container and the small holes in the wall of the buffer chamber, thereby restoring the balance between the tubular void and the pressure of the inner tubular container.

如果管状空隙中的压力升冲，少量的含Fe+离子的碱溶液将通过它壁上的小孔进入缓冲室，随之便与缓冲室中的碱溶液混合，此碱溶液中的Fe+离子也被稀释了，然后再进入内管状容器此稀释后的碱溶液仅对内管状容器中的晶种产生极小的影响。此外，管状空隙中的碱溶液浓度也足够低以至对容器体的内表面无腐蚀作用。由于这种作用，降低了Fe+离子产生，从而进一步减少了内管状容器中对晶种的有害影响。If the pressure in the tubular gap rises, a small amount of alkaline solution containing Fe + ions will enter the buffer chamber through the small hole on its wall, and then mix with the alkaline solution in the buffer chamber, and the Fe + ions in the alkaline solution will It has also been diluted before entering the inner tubular container. This diluted alkaline solution has only minimal impact on the seed crystals in the inner tubular container. Furthermore, the concentration of the alkaline solution in the tubular space is low enough to have no corrosive effect on the inner surface of the container body. Due to this effect, the production of Fe + ions is reduced, thereby further reducing the detrimental effect on the seeds in the inner tubular container.

如在管状空隙中填充导热性能好的透气性材料，这不仅使从容器体到内管状容器的传热效果得到改善，也使内管状容器中的压力等于外部压力。If the air-permeable material with good thermal conductivity is filled in the tubular space, this not only improves the heat transfer effect from the container body to the inner tubular container, but also makes the pressure in the inner tubular container equal to the external pressure.

参照图1-3来对本发明的实施方案进行说明，图1是一根据本发明的实施方案，用于水热合成用容器的半剖面图。该容器包括以下主要部件;由高强度，高韧性，耐腐蚀的金属材料制备的，由外部加热的容器体1，容器体盖2，它借助密封件2a和若干夹紧件3可活动地装于容器体1上，和由如银、金或铂一类贵金属制备的或由其内表面上用贵金属包层钛之类非贵金属制的底部内管状容器4。此内管状容器有活动盖4a和底板4b，它们是由和内管状容器同样的材料制备的。如图2所示，小孔4a′基本上位于盖4a的中心部位。小孔4a′的大小应使无任何压力作用在其上面，液体由于其表面张力不会因它自身的重量而下流。作为一种导向作用，此孔的直径约为0.4mm。缓冲室5是通过盖于小孔4a′上并固定在内管状容器盖4a上表面的盒状件5a所形成的。盒状件5a的顶板上带有一直径约为0.4mm的小孔5b。小孔5b的位置应比缓冲室5中的液面高。至少缓冲室5的内表面应由贵金属制备。Embodiments of the present invention will be described with reference to FIGS. 1-3. FIG. 1 is a half-sectional view of a container for hydrothermal synthesis according to an embodiment of the present invention. The container includes the following main components: a container body 1 made of high-strength, high-toughness, corrosion-resistant metal material, externally heated, and a container body cover 2, which is movably mounted by means of a sealing member 2a and a plurality of clamping members 3 On the container body 1, and a bottom inner tubular container 4 made of a noble metal such as silver, gold or platinum or a non-precious metal such as titanium clad with a noble metal on its inner surface. The inner tubular container has a movable cover 4a and a bottom plate 4b, which are made of the same material as the inner tubular container. As shown in FIG. 2, the small hole 4a' is located substantially at the center of the cover 4a. The size of the small hole 4a' is such that without any pressure acting on it, the liquid will not flow down due to its own weight due to its surface tension. As a guide, the diameter of this hole is about 0.4 mm. The buffer chamber 5 is formed by a box-like member 5a that covers the small hole 4a' and is fixed to the upper surface of the inner tubular container lid 4a. A small hole 5b having a diameter of about 0.4mm is formed on the top plate of the box-like member 5a. The position of the small hole 5b should be higher than the liquid level in the buffer chamber 5 . At least the inner surface of the buffer chamber 5 should be made of noble metal.

将其结构如上所述的内管状容器4放于容器体1中，但它们之间保持一管状空隙1a。The inner tubular container 4 having the structure as described above is placed in the container body 1 with a tubular space 1a maintained therebetween.

图1所示的容器也有两个对流控制板6a和6b。板6a在内管状容器4之内，板6b在内管状容器4和容器体1间的管状空隙1a中。晶种放于对流控制板6a上方的内管状容器4中，原料放于对流控制板的下方。缓冲室5的空间，容器体1和内管状容器4间的管状空隙1a的有效空间及内管状容器4的有效空间装有特定比例的碱溶液，应使缓冲室5和管状空隙1a中的碱溶液浓度低于内管状容器4中的碱溶液浓度。The vessel shown in Figure 1 also has two convection control panels 6a and 6b. The plate 6a is inside the inner tubular container 4 and the plate 6b is in the tubular space 1a between the inner tubular container 4 and the container body 1 . The seed crystal is placed in the inner tubular container 4 above the convection control plate 6a, and the raw material is placed below the convection control plate. The space of the buffer chamber 5, the effective space of the tubular space 1a between the container body 1 and the inner tubular container 4 and the effective space of the inner tubular container 4 are equipped with a specific ratio of alkaline solution, the alkali in the buffer chamber 5 and the tubular space 1a should be The concentration of the solution is lower than that of the alkaline solution in the inner tubular container 4 .

在上述条件下，从外部加热容器体1以引发水热合成。Under the above conditions, the container body 1 was heated from the outside to initiate hydrothermal synthesis.

本发明的容器按如下方法进行操作，缓冲室5经由小孔5b与管状空隙1a相通，经由小孔4a′与内管状容器4的内部相通。这样，如果由于管状空隙1a和内管状容器4中流体的比例略与规定值不同或由于加热而在管状空隙1a和内管状容器4的流体间引起温度差使内管状容器4中的压力与外压不同时，缓冲室5中碱溶液将流入内管状容器4中或流入管状空隙1a中以使内管状容器4中的压力和外压恢复平衡。The container of the present invention operates in such a way that the buffer chamber 5 communicates with the tubular space 1a via the small hole 5b and communicates with the interior of the inner tubular container 4 via the small hole 4a'. Like this, if the ratio of the fluid in the tubular space 1a and the inner tubular container 4 is slightly different from the prescribed value or due to heating, a temperature difference is caused between the fluids in the tubular space 1a and the inner tubular container 4 so that the pressure in the inner tubular container 4 is different from the external pressure. At different times, the alkaline solution in the buffer chamber 5 will flow into the inner tubular container 4 or into the tubular space 1a to restore the balance between the pressure in the inner tubular container 4 and the external pressure.

而且，管状空隙1a中含Fe+离子的碱溶液进入内管状容器4之前就与缓冲室5中的碱溶液混合，所以使进入内管状容器4中的碱溶液中的Fe+离子得到了充分的稀释，而将对于最终产品质量的可能的有害影响减至最小。And, before the alkaline solution containing Fe + ions in the tubular space 1a enters the inner tubular container 4, it is mixed with the alkaline solution in the buffer chamber 5, so the Fe + ions in the alkaline solution entering the inner tubular container 4 are fully enriched. dilution while minimizing possible adverse effects on the quality of the final product.

将管状空隙1a中的碱溶液浓度调到低于内管状容器4中的浓度，这便有效降低了容器体1的腐 蚀及Fe+离子的产生。The concentration of the alkali solution in the tubular space 1a is adjusted to be lower than that in the inner tubular container 4, which effectively reduces the corrosion of the container body 1 and the generation of Fe + ions.

与图2所示结构不同的缓冲室5示于图3。此缓冲室是由固定在内管状容器的盖4a下侧的并将小孔4a′盖上的盒状件5′所形成的。小孔5′b的直径约0.4mm，在盒状件5′a的侧板上，位于此缓冲室的液面之上。此缓冲室5′优选内外表面均用贵金属制备。A buffer chamber 5 having a structure different from that shown in FIG. 2 is shown in FIG. 3 . This buffer chamber is formed by a box-like member 5' fixed to the underside of the lid 4a of the inner tubular container and covering the aperture 4a'. The diameter of the small hole 5'b is about 0.4mm, on the side plate of the box-like part 5'a, above the liquid level of the buffer chamber. The buffer chamber 5' is preferably made of noble metal on both inner and outer surfaces.

经小孔4a″流入缓冲室5′的含Fe+离子的碱溶液将与此缓冲室中的碱溶液混合。此碱溶液中的Fe+离子在被充分稀释后再进入内管状容器4。这样缓冲室5′基本上将起到与缓冲室5同样的效果。The alkaline solution containing Fe + ions that flows into the buffer chamber 5' through the aperture 4a "will be mixed with the alkaline solution in this buffer chamber. The Fe + ions in this alkaline solution will enter the inner tubular container 4 after being fully diluted. Like this The buffer chamber 5' will basically have the same effect as the buffer chamber 5.

从容器体1到内管状容器4最好进行有效的热传递。因此，管状空隙1a的宽度对热传递有不利影响，最好在管状空隙1a中填充以导热性能好的，透气性的，热膨胀率高的泡沫金属镍之类的材料。为了使管状空隙1a中的压力均匀，所以要求透气率高。为了使容器体1的内表面和内管状容器4的外表面随温度的升高而获得粘附良好的效果，所以要求热膨胀率高。Efficient heat transfer from the vessel body 1 to the inner tubular vessel 4 is preferred. Therefore, the width of the tubular space 1a has an adverse effect on heat transfer, and it is better to fill the tubular space 1a with materials such as nickel foam with good thermal conductivity, gas permeability, and high thermal expansion rate. In order to make the pressure in the tubular space 1a uniform, a high air permeability is required. In order for the inner surface of the container body 1 and the outer surface of the inner tubular container 4 to achieve a good adhesion effect with increasing temperature, a high coefficient of thermal expansion is required.

从上面的解释中会明白本发明的容器具有下列优点：From the above explanation, it will be clear that the container of the present invention has the following advantages:

（1）使用此容器，其中放有晶种的内管状容器将不会产生Fe+离子。(1) With this container, the inner tubular container in which the seed crystals are placed will not generate Fe + ions.

（2）内管状容器的壁相当薄，但能使其中的压力与外压保持平衡，从而能确保操作稳定而不致使内管状容器变形或损坏。(2) The wall of the inner tubular container is relatively thin, but the pressure therein can be kept in balance with the external pressure, so that stable operation can be ensured without deformation or damage of the inner tubular container.

（3）在容器体被碱溶液腐蚀时，会产生Fe+离子。然而，如果内管状容器外部的压力升高，所产生的Fe+离子被缓冲室中的碱溶液适当稀释后，碱溶液才流入内管状容器，所以Fe+离子对内管状容器中的晶种的影响是轻微的。(3) When the container body is corroded by alkaline solution, Fe + ions will be generated. However, if the pressure outside the inner tubular container increases, the produced Fe + ions are properly diluted by the alkaline solution in the buffer chamber before the alkaline solution flows into the inner tubular container, so the Fe + ions have a positive effect on the seed crystals in the inner tubular container. The impact is slight.

（4）与容器体接触的碱溶液浓度如此低，以至于对容器体的腐蚀作用小到足以能减少Fe+的产生。(4) The concentration of the alkaline solution in contact with the container body is so low that the corrosion effect on the container body is small enough to reduce the production of Fe + .

鉴于上述优点，本发明的容器能使水热合成法生产水晶和其它产品质地优良。In view of the above advantages, the container of the present invention enables hydrothermal synthesis to produce crystals and other products of good quality.

Claims (6)

1、一种碱性液中水热合成用容器，其特征在于所说容器包括：1. A container for hydrothermal synthesis in alkaline liquid, characterized in that said container comprises: 从外部加热的容器体；Vessel body heated externally; 置于所说容器体中并于其间形成一管状空隙的内管状容器，所说内管状容器的内表面是由诸如银、金或铂一类贵金属制备的，此容器有一其上带有第一小孔的盖；An inner tubular container disposed within said container body and forming a tubular space therebetween, said inner tubular container having an inner surface made of a precious metal such as silver, gold or platinum, having a first small hole cover; 用以将所说的第一小孔盖上的缓冲室，所说的缓冲室有一为所说的盖限定的壁，此缓冲室的另一壁上有第二个小孔；a buffer chamber for covering said first aperture, said buffer chamber having a wall defined by said cover, and a second aperture on the other wall of said buffer chamber; 所说缓冲室的空间、所说管状空隙的有效空间及所说内管状容器的有效空间分别装有特定比例的碱溶液，所说缓冲室及所说管状空隙中的碱溶液浓度比所说内管状容器中的碱溶液浓度低；The space of said buffer chamber, the effective space of said tubular void and the effective space of said inner tubular container are respectively equipped with a certain proportion of alkali solution, and the concentration of alkali solution in said buffer chamber and said tubular void is higher than that of said inner tubular container. The alkaline solution in the tubular container has a low concentration; 在所说容器体和所说内管状容器之间的所说管状空隙中装有导热性能好的透气性材料。A gas-permeable material with good thermal conductivity is installed in the tubular space between the container body and the inner tubular container. 2、根据权利要求1所述的容器，其特征在于其中所说的缓冲室在所说内管状容器的外部。2. The container of claim 1 wherein said buffer chamber is external to said inner tubular container. 3、根据权利要求1所述的容器，其特征在于其中所说的缓冲室在所说内管状容器的内部。3. The container of claim 1, wherein said buffer chamber is inside said inner tubular container. 4、根据权利要求1所述的容器，其特征在于其中所说的第二小孔位于装有所说缓冲室的碱溶液液面上方。4. The container of claim 1, wherein said second aperture is located above the level of the alkaline solution containing said buffer chamber. 5、根据权利要求2所述的容器，其特征在于其中所说缓冲室有一由贵金属制备的内表面。5. The container of claim 2, wherein said buffer chamber has an inner surface formed of a noble metal. 6、根据权利要求3所述的容器，其特征在于其中所说缓冲室的内、外表面均是由贵金属制备的。6. The container according to claim 3, wherein the inner and outer surfaces of said buffer chamber are made of noble metal.
CN90101411.7A 1988-08-05 1990-02-03 container for hydrothermal synthesis Expired - Fee Related CN1022335C (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP63194338A JPH0722692B2 (en) 1988-08-05 1988-08-05 Hydrothermal synthesis container
CN90101411.7A CN1022335C (en) 1988-08-05 1990-02-03 container for hydrothermal synthesis
DE4003377A DE4003377C1 (en) 1988-08-05 1990-02-05

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JP63194338A JPH0722692B2 (en) 1988-08-05 1988-08-05 Hydrothermal synthesis container
CN90101411.7A CN1022335C (en) 1988-08-05 1990-02-03 container for hydrothermal synthesis

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CN1053819A CN1053819A (en) 1991-08-14
CN1022335C true CN1022335C (en) 1993-10-06

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US5552039A (en) 1994-07-13 1996-09-03 Rpc Waste Management Services, Inc. Turbulent flow cold-wall reactor
JP3366820B2 (en) * 1997-02-19 2003-01-14 株式会社日立製作所 Oxidation treatment method and apparatus and reaction vessel
SE518803C2 (en) 1999-09-03 2002-11-26 Chematur Eng Ab Method and reaction system with high pressure and high temperature suitable for supercritical water oxidation
US6398867B1 (en) * 1999-10-06 2002-06-04 General Electric Company Crystalline gallium nitride and method for forming crystalline gallium nitride
PL207400B1 (en) 2001-06-06 2010-12-31 Ammono Społka Z Ograniczoną Odpowiedzialnością Method of and apparatus for obtaining voluminous, gallium containing, monocrystalline nitride
KR100850293B1 (en) 2001-06-06 2008-08-04 니치아 카가쿠 고교 가부시키가이샤 Process and appratus for obtaining bulk monocrystalline gallium-containing nitride
JP2003063889A (en) * 2001-08-24 2003-03-05 Tokyo Denpa Co Ltd Vessel for growing single crystal
DE60234856D1 (en) 2001-10-26 2010-02-04 Ammono Sp Zoo SUBSTRATE FOR EPITAXIA
KR100679377B1 (en) 2001-10-26 2007-02-05 암모노 에스피. 제트오. 오. Light Emitting Device Structure Using Nitride Bulk Monocrystalline Layer
US7335262B2 (en) 2002-05-17 2008-02-26 Ammono Sp. Z O.O. Apparatus for obtaining a bulk single crystal using supercritical ammonia
PL225427B1 (en) 2002-05-17 2017-04-28 Ammono Spółka Z Ograniczoną Odpowiedzialnością Light emitting element structure having nitride bulk single crystal layer
CN1297695C (en) * 2003-04-25 2007-01-31 郎丽红 Autoclave for artificial quartz crystal
JP4276627B2 (en) 2005-01-12 2009-06-10 ソルボサーマル結晶成長技術研究組合 Pressure vessel for single crystal growth and method for producing the same
CN112442730A (en) * 2019-08-29 2021-03-05 桂林百锐光电技术有限公司 Device for growing large-size single crystal by temperature difference hydrothermal method

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JPH0243939A (en) 1990-02-14

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