CN106470811A - 用于等离子体熔融的喷涂干燥混合的批料材料 - Google Patents

用于等离子体熔融的喷涂干燥混合的批料材料 Download PDF

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CN106470811A
CN106470811A CN201580036360.XA CN201580036360A CN106470811A CN 106470811 A CN106470811 A CN 106470811A CN 201580036360 A CN201580036360 A CN 201580036360A CN 106470811 A CN106470811 A CN 106470811A
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spraying drying
slurry
spraying
carry out
granule
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J·A·海涅
I·M·彼得森
J·F·小怀特
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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
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/026—Pelletisation or prereacting of powdered raw materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B1/00—Preparing the batches
    • C03B1/02—Compacting the glass batches, e.g. pelletising
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/1005—Forming solid beads
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/1005—Forming solid beads
    • C03B19/102—Forming solid beads by blowing a gas onto a stream of molten glass or onto particulate materials, e.g. pulverising
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/002—Hollow glass particles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
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  • Glass Compositions (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

一种制备用于喷涂干燥和后续熔融如通过等离子体熔融的稳定的玻璃前体颗粒浆料的方法，所述方法包括将所有成分颗粒磨碎到尺寸小于50微米，更理想地磨碎到尺寸小于25微米或甚至小于20微米，从颗粒除去水或降低颗粒的水分含量，在20‑30体积％、更具体的22‑27体积％、更理想地24体积％的固体装载下，将颗粒与液体聚合物粘合剂和分散剂混合。

Description

用于等离子体熔融的喷涂干燥混合的批料材料
相关申请交叉参考
本申请根据35U.S.C.§119要求2014年07月02日提交的美国临时申请系列第62/020,390号的优先权，本文以该申请的内容为基础并通过参考将其完整地结合于此。
技术领域
本公开总体涉及玻璃制造和方法，具体来说，涉及包括喷涂干燥混合的批料材料，然后进行等离子体熔融的玻璃方法。
背景
已知等离子体熔融细分玻璃前体作为制备玻璃的一种方法。已知通过喷涂干燥来制备用于等离子体熔融的玻璃前体的聚集体。用于喷涂干燥的浆料的典型制备依靠调节颗粒浆料的pH，从而在颗粒之间提供一定程度的静电互斥。
概述
公开一种制备用于后续喷涂干燥的稳定玻璃前体颗粒浆料的方法。所述方法可且理想地的确包括研磨所有成分颗粒，理想地磨碎到尺寸小于50微米，且更理想地磨碎到尺寸小于25微米或甚至小于20微米。这增加所得悬浮液的稳定性。此外，所述方法包括对于至少是吸湿的那些颗粒和/或形成氢氧化物的那些颗粒而言，从颗粒除去水分或减少颗粒的水分含量。然后，将颗粒与液体聚合物粘合剂和分散剂混合，理想地通过首先将这些混合进入水中，然后添加颗粒并进行混合来形成浆料。分散剂有助于防止颗粒在喷涂干燥之前聚集，同时粘合剂在喷涂干燥过程中干燥来将聚集体固定在一起。浆料的固体装载理想地是20-30体积％，更具体的22-27体积％，最理想地24体积％。然后，在喷涂干燥之后，这个方法能制备总体球形的聚集体，且聚集体颗粒的模式(mode)是小于或等于100微米，理想地是约50±10微米，更理想地约50±5微米。
附图简要说明
当参考附图阅读下面的详细描述时将更好地理解这些和其它方面，其中：
图1显示在形成浆料之前理想的玻璃成分的颗粒分布的示例；
图2是通过所公开和所述方法制备的聚集体的一种实施方式的电子显微图片；
图3显示在喷涂干燥之后且在等离子体熔融来制备玻璃之前的聚集体的理想的颗粒分布的示例；
图4是SEM背散射图像，其显示通过等离子体熔融用根据本公开的方法制备的喷涂干燥的球制备的组成均匀的等离子体熔融球的抛光的横截面；
图5是SEM背散射图像，其显示通过替代方法制备的类似制备的组成非均匀的等离子体熔融球。
具体描述
在此将参照附图更完整地描述示例，附图中给出了各种示例实施方式。只要有可能，在所有附图中使用相同的附图标记来表示相同或类似的部分。但是，这些方面可以以许多不同的方式实施，不应被解读成局限于在此提出的实施方式。
具有制备尺寸小于100微米的单个聚集体的方法是有用的，所述聚集体包含良好分布、比例正确且可用于制备例如Eagle玻璃的玻璃的原料批料材料的混合物，包括二氧化硅、氧化铝、SrCO3、CaCO3、B2O3、MgO和SnO2。
聚集体通常通过喷涂干燥来制备。为了喷涂干燥批料，应该制备含有所有批料材料的均匀分散的悬浮液。通常这通过调节pH来进行，从而pH值远离等电位点。但是，用于Eagle玻璃和一些其它玻璃的配料中所用的批料材料具有较宽的各种等电位点，如从下文的表1中的数值(从文献中获得)可知，从而使用这种方法来制备均匀、良好性能浆料不太可行。本公开描述和披露一种用于制备和稳定用于组分(例如这些组分)的混合物的混合的组分浆料以及成功地将它喷涂干燥成所需尺寸范围的球形聚集体的方法，
表I
本文所述的制备稳定浆料的方法涉及将颗粒磨碎到尺寸至少小于50微米，理想地小于25微米或甚至小于20微米。这增加悬浮液中颗粒的稳定性。参考图1，显示了理想的粒度分布的一种实施方式的示例，其可用作用于本公开的方法的起始粒度。干燥颗粒，或干燥至少那些形成氢氧化物或以其它方式吸湿的那些颗粒。在本文所述的实验实施例中，将它们在90℃下的热空气干燥器中干燥5-10小时。
接下来，理想地混合或搅拌水，且当在混合或搅拌水时，将液体聚合物基粘合剂和分散剂添加到水。然后，将固体缓慢地添加到液体，同时连续地混合或搅拌从而用一层聚合物分散剂涂覆颗粒，以提供在喷涂干燥之前抗拒聚集的空间位阻，以及还用粘合剂材料涂覆颗粒，该粘合剂材料在喷涂干燥过程中干燥，从而将喷涂干燥的聚集体固定在一起。浆料的固体装载理想地是20-30体积％，更具体的22-27体积％，更理想地约24体积％。在本文所述的实验实施例中，使用在500RPM下开始的混合机在烧杯中混合水，然后将5重量％的液体聚合物基粘合剂(苯乙烯丙烯酸共聚物，例如Duramax B1022)和0.045重量％分散剂(丙烯酸聚合物的铵盐，例如Duramax D3005)添加到水，同时混合。然后，对于总计10000克浆料，以24体积％的颗粒负载，将固体缓慢地添加到液体，全部在连续搅拌地同时添加，在颗粒添加之后最高达1200RPM，从而用一均匀的聚合物分散剂层涂覆颗粒，以提供在喷涂干燥之前抗拒聚集的空间位阻，以及用粘合剂涂覆颗粒，该粘合剂在喷涂干燥过程中干燥，从而将喷涂干燥的聚集体固定在一起。
然后，对浆料进行喷涂干燥，理想地在100-120℃的出口温度下(实验中在104℃下)，且在250-350℃的进口温度下(实验中在300℃下)，以及理想地在1巴(bar)±20％、理想地±10％的雾化压力下(实验中和标称的1巴)。使用具有双流体喷泉喷嘴系统的GEAMobile Minor喷涂干燥器。
图2是所得球形聚集体的电子显微图片。
图3是聚集体尺寸分布的图片，且聚集体颗粒的模式为小于或等于100微米、是约50±5微米或约50±10微米。已显示制备的聚集体的等离子体熔融能形成尺寸从纳米变化到微米的Eagle玻璃球。
图4是SEM背散射图像，其显示通过等离子体熔融用根据本公开的方法制备的喷涂干燥的球制备的组成均匀的等离子体熔融球。这样制备的均匀的球可用于制备具有所有形状和形式的本体玻璃物体，例如通过模塑、烧结、3D打印等。
图5是SEM背散射图像，其显示通过等离子体熔融用替代方法制备的喷涂干燥的球制备的组成不均匀的等离子体熔融球。
本领域的技术人员显而易见的是，可以在不偏离所要求保护主题的范围和精神的情况下对本发明进行各种修改和变动。

Claims (15)

1.一种制备用于喷涂干燥的稳定的玻璃前体颗粒浆料的方法，所述方法包括以下步骤：
将前体颗粒研磨到尺寸小于50微米；
从所述颗粒除去水，或者降低所述颗粒的水分含量；以及
将干燥的颗粒与液体聚合物粘合剂和液体分散剂混合，以形成浆料。
2.如权利要求1所述的方法，其特征在于，研磨步骤包括将所有前体颗粒研磨到尺寸小于25微米。
3.如权利要求1所述的方法，其特征在于，研磨步骤包括将所有前体颗粒研磨到尺寸小于20微米。
4.如权利要求1-3中任一项所述的方法，其特征在于，混合步骤包括首先将液体聚合物粘合剂和液体分散剂混合进入水中，然后添加所述颗粒并进行混合来形成所述浆料。
5.如权利要求1-4中任一项所述的方法，其特征在于，混合步骤还包括按比例混合，从而获得20-30体积％的浆料的固体装载。
6.如权利要求1-4中任一项所述的方法，其特征在于，混合步骤还包括按比例混合，从而获得22-27体积％的浆料的固体装载。
7.如权利要求1-4中任一项所述的方法，其特征在于，混合步骤还包括按比例混合，从而获得约24体积％的浆料的固体装载。
8.如权利要求1-7中任一项所述的方法，其特征在于，所述方法还包括下述步骤：喷涂干燥所述浆料。
9.如权利要求8所述的方法，其特征在于，喷涂干燥步骤包括在100-120℃的出口温度下进行喷涂干燥。
10.如权利要求8所述的方法，其特征在于，喷涂干燥步骤包括在104℃的出口温度下进行喷涂干燥。
11.如权利要求8-10中任一项所述的方法，其特征在于，喷涂干燥步骤包括在250-350℃的进口温度下进行喷涂干燥。
12.如权利要求8-10中任一项所述的方法，其特征在于，喷涂干燥步骤包括在300℃的进口温度下进行喷涂干燥。
13.如权利要求8-12中任一项所述的方法，其特征在于，喷涂干燥步骤包括在1巴±20％的雾化压力下进行喷涂干燥。
14.如权利要求8-12中任一项所述的方法，其特征在于，喷涂干燥步骤包括在1巴±10％的雾化压力下进行喷涂干燥。
15.如权利要求8-12中任一项所述的方法，其特征在于，喷涂干燥步骤包括在1巴的雾化压力下进行喷涂干燥。
CN201580036360.XA 2014-07-02 2015-06-30 用于等离子体熔融的喷涂干燥混合的批料材料 Pending CN106470811A (zh)

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