Name: protocol for measuring the thermal properties of a supercooled synthetic sand-water-gas-methane hydrate sample
Uploaded: 2016-03-21T15:00:00.000+00:00
Duration: 9 min 46 s
Description: Watch this Scientific Journal Video about Protocol for Measuring the Thermal Properties of a Supercooled Synthetic Sand-water-gas-methane Hydrate Sample at JoVE.com

这项研究是财政上MH21研究联盟甲烷水合物资源日本经济，贸易和工业部国家甲烷水合物开发计划的支持。笔者想感谢T.前川和S.转到他们与实验的援助。 经许可后转载自数字（村冈，M.，Susuki，N.，山口，H.，辻，T.，山本，Y.，能源燃料，29（3），2015年，1345年至1351年，2015年，DOI: 10.1021 / ef502350n）。版权所有（2015）美国化学学会。

注:请查阅所有相关的材料安全数据表作为本研究采用高压可燃甲烷气体和大型高压容器。戴上头盔，护目镜和防护靴。如果温度控制系统停止，在容器内的压力与氢离解增加而增加。为了防止发生意外，强烈建议使用安全阀系统自动甲烷气体释放到大气中。安全阀系统可以在没有电源供给工作。 1.沙-水-甲烷气体样品9的制备<ol><li>放置高压容器上的振动台上。 </li><li>倾1.5升纯水中水瓶，4000克二氧化硅砂在砂瓶中。准确称取沙子和水的群众在沙和水的瓶子，分别。 </li><li>倒入1升纯水中的高压容器从水瓶2,110 cm 3的内部容积直到水填满半内部容器。 </li><li>打开振动台振动整个容器。设置振动速度和电源以分别为50赫兹和220瓦，。施加振动，直到步骤1.5的完成。通过振动容器移除在容器的底部的漏极线及烧结金属过滤器的残留空气。 </li><li>倾从砂瓶子进入容器3300克硅砂在约1g秒的恒定速率-1使用而整个容器被振动，以确保均匀的填料的水表面附近保持的漏斗。 </li><li>停止振动时水到达容器的边缘。 </li><li>放置一个环作为在容器上，以防止水溢出的边缘暂时壁。 </li><li>在50赫兹和220 W.再次振动该容器</li><li>当沙到达容器（高度140毫米）的边缘，关闭振动。 </li><li>删除使用次临时墙，孔隙水Ë排水管线。倒入孔隙水回水瓶。 </li><li>在50赫兹和300瓦1秒钟一次或两次振动容器包装的沙子，如果需要添加更多的沙子。 </li><li>称取沙子和水的群众在沙和水瓶。计算沙子和水团从沙子和水的瓶子质量差异的船只。在这个实验中，沙子和水的容器中的群众分别3385克和823.6克。的水在容器内的质量被表示为W 总 。 </li><li>覆盖高压容器用不锈钢盖，拧紧对角线相对的对的螺栓序列。 </li><li>从振动台移动至高压容器，以用于实验中的表。 </li><li>覆盖高压容器与热绝缘体，用于控制温度。 </li><li>高压管道和冷却水流线连接到高压容器中。 </li&gt; <li>开的输入和输出的气体管线的阀。在800毫升分钟-1的速度，直至没有过量的水排放入大气压力下的陷阱通风10升甲烷。砂放电被固定在容器的底部的烧结金属过滤器防止。残留的水保留在砂表面上因为亲水硅砂吸附的水分子。 </li><li>权衡的水的质量在陷阱，W 陷阱 ，以确定容器中的气体体积。确定的残留水，W 资源利用公式群众，在血管W¯¯RES = W 总 - 含 陷阱 。在这种情况下，W 水库以及w 阱分别360.6克和463.0克。 </li><li> V 砂 / V 细胞 ，其中V 沙 T的音量-使用公式Ѱ= 1确定样品的孔隙率由砂质量与砂密度（ 即 ，ρS =2630公斤米-3），和V 细胞的比率来确定他沙是在容器的内部容积。样品的孔隙率Ѱ为0.39。 </li><li>关闭输出天然气管线的阀门。注入甲烷，以增加甲烷的孔隙压力在容器到约1210兆帕，在室温（ 即 31.6℃）。 </li><li>关闭输入气体管线的阀。 </li><li>开始使用数据记录器在实验过程中记录在容器内的压力和温度。数据采样的时间间隔为5秒。总的实验时间约为3000分钟。 </li></ol> 2. MH合成和热性能"过冷样品9测量<ol><li>打开冷却器用于通过循环冷却剂从室温容器冷却至2.0℃。让我们从冷却器T中的冷却液循环Ó容器的底部，从那里到容器的盖子，并最后返回到冷却器。在容器中的温度变化率约为0.001℃，秒-1。 </li><li>设置使用TPS分析软件测量参数。设置传感器类型传感器设计＃7577。设置的输出功率W 0至30毫瓦和测量时间为5秒。请注意，如果传感器类型或样品条件改变相应参数应该改变。设置参数以从1℃的提高温度至1.5℃。 </li><li>计算过冷，ΔTSUP，用下面的方程式的程度: SUPΔT= T EQ（P） - T的。 （3） Ť 当量 （P）为MH的平衡温度为压力P的函数Ť 当量 （P）的是使用CSMGem软件1进行计算。0; P和T是通过使用压力和温度计，分别测量该容器中的压力和温度。 </li><li>使用TPS分析器后ΔTSUP大于2℃同时测量热导率，热扩散率，和体积比热。 </li><li>切换连接到每个测量后的热性能分析器TPS的探针。开关实验9在TPS探头和手动分析仪之间的电缆。连接图显示在图中的S2参考9。每个传感器的切换顺序是否定的。 6→2→7→5→1→9→4→3→8→6 ...。该序列是根据在传感器之间的距离，这是设置尽可能防止影响测量的余热。收集数据每3-5分钟。 </li><li>重复测量，直到＆＃916;吨燮 达到200°再次℃。在该实验中，ΔŤSUP最初随着时间而增加。后ΔTSUP达到最大值，因为压力带MH的形成减小ΔTSUP逐渐减小到0℃。检查，如果ΔTSUP是之前使用等式3在TPS测量大于2℃。 </li><li>确保该温度分布不受MH熔化。如果氢在测量过程中熔化时，温度不会增加，因为氢的熔化是吸热反应。在测量过程中检查的温度分布，并在结果部分进行了讨论。 </li><li>使用TPS技术，所有的温度分布的数据进行热性能"分析。 </li></ol> 3.样品9,11的饱和度变化的计算注意:饱和为氢，水和气体的样品作为时间t的函数的程度使用的气体的状态方程来计算。所使用的计算的细节和方程先前所述11。 <ol><li>计算出的甲烷气体体积V 气体 ， 叔在时间t <img alt="公式4" src="/files/ftp_upload/53956/53956eq4.jpg" /> 其中Q是气体的容器中的初始体积V MH，叔- 1是氢的在时刻t的体积- 1，和R VHW是水和MH的体积比。 <img alt="公式5" src="/files/ftp_upload/53956/53956eq5.jpg" /> 在公式5 中，n是MH的水合数（〜6），ρMH，ρ 水分别对应于氢和水的密度，以及w MH和w的 水表示氢和水，r的分子质量espectively。 </li><li>计算量ΔM 吨 （摩尔）MH的从T形成- 1到T <img alt="公式6" src="/files/ftp_upload/53956/53956eq6.jpg" /> 其中，R是气体常数，P为甲烷气体的压力，和Z 吨 （T 气体 ，T，P 的气体 ，t）是甲烷的在时刻t的压缩系数。我们9和坂本等 11所使用的本尼迪克特-韦布-鲁宾（BWR）方程，Lee和凯斯勒改性，计算ž 牛逼 12，13。对于这个计算，公式（3-7.1） - 7参考13 - BWR的13式和李-凯斯勒常数（3-7.4）在表3中。 </li><li>计算体积变化ΔV MH， <suB&gt;从T MH的笔- 1到T <img alt="公式7" src="/files/ftp_upload/53956/53956eq7.jpg" /> 其中P 小号 是101325 Pa的基准压力，T s是273.15 K时的基准温度中，Z s是在P点S中的压缩系数和T 秒 （ŽS〜1）和V CH 4是在甲烷气体体积的比率MH的单位体积[米3米-3。使用的165.99为V CH4值[米3米-3。 </li><li>计算体积V MH， 叔 MH的在时间t <img alt="式（8）" src="/files/ftp_upload/53956/53956eq8.jpg" /></li><li>计算水中v 水在压力容器的体积， 叔在时间t <img alt="公式9" src="/files/ftp_upload/53956/53956eq9.jpg" /&gt; 其中V 水，1是水的初始体积。 </li><li>重复使用公式计算。 4-9在时间t = 2，3，...，以确定在水，甲烷，和MH 11的饱和的变化。初始条件为t = 1， 即 ，V 气体 ，1 = Q。 t时刻的P和T是从数据日志9服用。计算结果示于下面的部分。 </li></ol>

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The authors have nothing to disclose.

估计MH的测量形成热的影响。 MH的形成热量从中文变化率的产品估计， 如图3b和形成H = 52.9千焦摩尔-1 MH 14的焓。因此，最高温度变化是0.00081℃，秒-1。这是比5秒的时间间隔期间1℃，1.5℃之间的TPS传感器的温度上升ΔTÇ低得多。详细的估计和讨论二段描述。 4参考9。 以下是至关重要的协议的步?...

天然气水合物是包含含有在轿厢1客体分子氢键的水分子的笼形结构的结晶化合物。在海底和永久冻土地区的甲烷水合物（MHS）的大量非常有趣的未来能源资源，但可能会影响到全球的气候条件2。 2013年3月，日本石油，天然气和金属国家公司进行了世界上第一个海上生产测试，使用了"减压法"3,4东部南海海槽自然承载MH沉积物中提取气体。 气体水合物可以存储气体，例如甲烷1，氢5，CO 2 1,6，和臭氧7。因此，甲烷和氢气水合物研究作为势能储存和运输介质。为了减少二氧化碳释放到大气中，CO 2 seques 2排放使用二氧化碳在深海沉积物2水合物tration进行了研究6。臭氧是目前在水净化和食品杀菌使用。臭氧保鲜技术的研究已进行了，因为它是化学上不稳定7。在水合物的臭氧浓度是在臭氧化水或冰7比要高得多。 为了开发天然含MH沉积物和基于水合物技术的天然气产量，就必须了解天然气水合物的热性能。然而，气体水合物含沉积物的热性质数据和模型研究很少8。 的"减压方法"可用于通过减少低于水合物稳定的孔隙压力以解离氢的沉积物孔隙空间。在这个过程中，沉淀物的孔隙空间的分量，从水和氢水，氢，和气体发生变化。热性能"测量后者条件是困难的，因为氢的熔化热可能会影响测量结果。为了解决这个问题，村冈等在氢形成9进行热性质"测量在过冷的条件。 与此视频协议中，我们解释过冷合成砂水煤气氢样品的测定方法。 图1示出用于测量人工甲烷水合物轴承沉积物的热性能的实验装置。安装是如图参考9相同。该系统主要包括一高压容器中，压力和温度的控制，以及测量系统的热性能。高压容器用140毫米的内径为140毫米的高度由圆柱形不锈钢的;其与死体积除去内部容积是2110厘米3，而其压力限制为15兆帕。该transie<html> nt的平面源（TPS）技术被用于测量热性能10。九与2.001毫米个人半径TPS探头放入容器内。九个探针9的布局示于图2中的参考9。在TPS探针被连接到热性能&#39;分析器用电缆和在实验过程中手动切换。在TPS传感器，连接图，和设置在容器的细节示于图S1中 ，图2和的支持信息3中参考9。 <img alt="图1" src="/files/ftp_upload/53956/53956fig1.jpg" /> 图1:该实验装置用于测量所述人工甲烷水合物轴承沉积物的热性能的数字是从参考9修改。3956fig1large.jpg"目标="_空白"&gt;点击此处查看该图的放大版本。 使用了TPS方法测量每个样品的热性能。该方法的原则在参照图10进行说明。在该方法中，依赖于时间的温度上升，ΔTAVE，是<img alt="式（1）" src="/files/ftp_upload/53956/53956eq1.jpg" />哪里<img alt="公式（2）" src="/files/ftp_upload/53956/53956eq2.jpg" />在等式1中，W 0是来自传感器的输出功率，r是传感器探头的半径，λ是样品的热导率，α为热扩散率，t是从电源供给开始的时间到传感器探头。D（τ）是一个无量纲时间相关的功能。τ </青霉&gt;由（αT/ R）1/2给出。在等式2中，m是TPS探针的同心环的数量和I 0是一个修正贝塞尔函数。样品的热导率，热扩散率和比热同时由施加到作为电源被供给到传感器探头的温度上升反演分析确定。

<table><tbody><tr><td>TPS thermal probe, Hot disk sensor</td><td>Hot Disk AB Co., Sweden</td><td>#7577</td><td>Kapton sensor type, sensor radius 2.001 mm</td></tr><tr><td>Hot disk thermal properties analyzer</td><td>Hot Disk AB Co., Sweden</td><td>TPS 2500&amp;nbsp;</td><td></td></tr><tr><td>Toyoura standard silica sand</td><td>Toyoura Keiseki Kogyo Co., Ltd., Japan</td><td>N/A</td><td></td></tr><tr><td>Methane gas, 99.9999%</td><td>Tokyo Gas Chemicals Co., Ltd., Japan</td><td>N/A</td><td>Grade 6&amp;nbsp;N, Volume 47&amp;nbsp;L, Charging pressure 14.7&amp;nbsp;MPa</td></tr><tr><td>Water Purification System, Elix Advantage 3</td><td>Merck Millipore., U.S.</td><td>N/A</td><td>5 M&amp;Omega; cm (at 25&amp;nbsp;&amp;deg;C) resistivity</td></tr><tr><td>Vibrating table, Vivratory packer</td><td>Sinfonia Technology Co. Ltd., Japan</td><td>VGP-60</td><td></td></tr><tr><td>Chiller, Thermostatic Bath Circulator&amp;nbsp;</td><td>THOMAS KAGAKU Co., Ltd., Japan</td><td>TRL-40SP</td><td></td></tr><tr><td>Coorant, Aurora brine</td><td>Tokyo Fine Chemical Co.,Ltd., Japan</td><td>N/A</td><td>ethylene glycol 71&amp;nbsp;wt%</td></tr><tr><td>Temparature gage</td><td>Nitto Kouatsu., Japan</td><td>N/A</td><td>Pt 100, sheath-type platinum resistance temperature detector</td></tr><tr><td>Pressure gage</td><td>Kyowa Electronic Instruments., Japan</td><td>PG-200 KU</td><td></td></tr><tr><td>Data logger</td><td>KEYENCE., Japan</td><td>NR-500</td><td></td></tr><tr><td>Mass flow controller</td><td>OVAL Co., Japan</td><td>F-221S-A-11-11A</td><td>Maximum flow 2,000&amp;nbsp;N&amp;nbsp;ml&amp;#8288;/&amp;#8288;M, maximum design pressure 19.6&amp;nbsp;MPa</td></tr></tbody></table>

protocol for measuring the thermal properties of a supercooled synthetic sand-water-gas-methane hydrate sample

Methane hydrates (MHs) are present in large amounts in the ocean floor and permafrost regions. Methane and hydrogen hydrates are being studied as future energy resources and energy storage media. To develop a method for gas production from natural MH-bearing sediments and hydrate-based technologies, it is imperative to understand the thermal properties of gas hydrates.
The thermal properties' measurements of samples comprising sand, water, methane, and MH are difficult because the melting heat of MH may affect the measurements. To solve this problem, we performed thermal properties' measurements at supercooled conditions during MH formation. The measurement protocol, calculation method of the saturation change, and tips for thermal constants' analysis of the sample using transient plane source techniques are described here.
The effect of the formation heat of MH on measurement is very small because the gas hydrate formation rate is very slow. This measurement method can be applied to the thermal properties of the gas hydrate-water-guest gas system, which contains hydrogen, CO2, and ozone hydrates, because the characteristic low formation rate of gas hydrate is not unique to MH. The key point of this method is the low rate of phase transition of the target material. Hence, this method may be applied to other materials having low phase-transition rates.

图2a示出了不受MH熔化。ΔTc是温度的变化，由于热常数&#39;测量的温度分布; 图2b示出了由氢熔化影响的温度分布。在图2b的配置文件不能通过方程1和2进行分析，因为这些方程通过假设稳定样品条件的。 图3a示出的压力，温度，和在容器中作为时间的函数过冷却...

Watch this Scientific Journal Video about Protocol for Measuring the Thermal Properties of a Supercooled Synthetic Sand-water-gas-methane Hydrate Sample at JoVE.com

Protocol for Measuring the Thermal Properties of a Supercooled Synthetic Sand-water-gas-methane Hydrate Sample

We present a protocol for measuring the thermal properties of synthetic hydrate-bearing sediment samples comprising sand, water, methane, and methane hydrate.

协议测量过冷的合成砂水 - 气 - 甲烷水合物样品的热性能

Methane hydrates (MHs) are present in large amounts in the ocean floor and permafrost regions. Methane and hydrogen hydrates are being studied as future ...

protocol-for-measuring-thermal-properties-supercooled-synthetic-sand

Research

JoVE Journal

Environment

8.8K 次观看.  National Institute of Advanced Industrial Science and Technology (AIST). We present a protocol for measuring the thermal properties of synthetic hydrate-bearing sediment samples comprising sand, water, methane, and methane hydrate.

视频: Protocol for Measuring the Thermal Properties of a Supercooled Synthetic Sand-water-gas-methane Hydrate Sample

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied.

We present a procedure to determine the metal-silicate partitioning of siderophile elements, emphasizing techniques that suppress the formation of metal inclusions in experiments for the noble metals. The results of these experiments are used to demonstrate the effect of core-formation on the highly siderophile element composition of the mantle.

金属硅酸盐分区在高压和高温:实验方法和协议，以抑制高亲铁元素元素夹杂物

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from ...

科研

化学

Thermal Scanning Conductometry (TSC) as a General Method for Studying and Controlling the Phase Behavior of Conductive Physical Gels

The thermal scanning conductometry protocol is a new approach in studying ionic gels based on low molecular weight gelators. The method is designed to follow the dynamically changing state of the ionogels, and to deliver more information and details about the subtle change of conductive properties with an increase or decrease in the temperature. Moreover, the method allows the performance of long term (i.e. days, weeks) measurements at a constant temperature to investigate the stability and durability of the system and the aging effects. The main advantage of the TSC method over classical conductometry is the ability to perform measurements during the gelation process, which was impossible with the classical method due to temperature stabilization, which usually takes a long time before the individual measurement. It is a well-known fact that to obtain the physical gel phase, the cooling stage must be fast; moreover, depending on the cooling rate, different microstructures can be achieved. The TSC method can be performed with any cooling/heating rate that can be assured by the external temperature system. In our case, we can achieve linear temperature change rates between 0.1 and approximately 10 &#176;C/min. The thermal scanning conductometry is designed to work in cycles, continuously changing between heating and cooling stages. Such an approach allows study of the reproducibility of the thermally reversible gel-sol phase transition. Moreover, it allows the performance of different experimental protocols on the same sample, which can be refreshed to initial state (if necessary) without removal from the measuring cell. Therefore, the measurements can be performed faster, in a more efficient way, and with much higher reproducibility and accuracy. Additionally, the TSC method can be also used as a tool to manufacture the ionogels with targeted properties, like microstructure, with an instant characterization of conductive properties.

Thermal Scanning Conductometry TSC as a General Method for Studying and Controlling the Phase Behavior of Conductive Physical Gels

The kinetics of the cooling process defines the properties of ionic gels based on low molecular weight gelators. This manuscript describes the usage of thermal scanning conductometry (TSC), which obtains full control over the gelation process, along with in situ measurements of the samples' temperature and conductivity.

热扫描电导 (TSC) 作为研究和控制导电物理凝胶相行为的一般方法

The thermal scanning conductometry protocol is a new approach in studying ionic gels based on low molecular weight gelators. The method is designed to ...

环境科学

Experimental Study of the Relationship Between Particle Size and Methane Sorption Capacity in Shale

The amount of adsorbed shale gas is a key parameter used in shale gas resource evaluation and target area selection, and it is also an important standard for evaluating the mining value of shale gas. Currently, studies on the correlation between particle size and methane adsorption are controversial. In this study, an isothermal adsorption apparatus, the gravimetric sorption analyzer, is used to test the adsorption capacity of different particle sizes in shale to determine the relationship between the particle size and the adsorption capacity of shale. Thegravimetric method requires fewer parameters and produces better results in terms of accuracy and consistency than methods like the volumetric method. Gravimetric measurements are performed in four steps: a blank measurement, preprocessing, a buoyancy measurement, and adsorption and desorption measurements. Gravimetric measurement is presently considered to be a more scientific and accurate method of measuring the amount of adsorption; however, it is time-consuming and requires a strict measuring technique. A Magnetic Suspension Balance (MSB) is the key to verify the accuracy and consistency of this method. Our results show that adsorption capacity and particle size are correlated, but not a linear correlation, and the adsorptions in particles sieved into 40 - 60 and 60 - 80 meshes tend to be larger. We propose that the maximum adsorption corresponding to the particle size is approximately 250 &#181;m (60 mesh) in the shale gas fracturing.

We use an isothermal adsorption apparatus, the gravimetric sorption analyzer, to test the adsorption capacity of different particle sizes of shale, in order to find out the relationship between particle size and the adsorption capacity of shale.

页岩中粒径与甲烷吸附能力关系的实验研究

The amount of adsorbed shale gas is a key parameter used in shale gas resource evaluation and target area selection, and it is also an important standard ...

An Experimental Protocol for Studying Mineral Effects on Organic Hydrothermal Transformations

Organic-mineral interactions are widely occurring in hydrothermal environments, such as hot springs, geysers on land, and the hydrothermal vents in the deep ocean. Roles of minerals are critical in many hydrothermal organic geochemical processes. Traditional hydrothermal methodology, which includes using reactors made of gold, titanium, platinum, or stainless-steel, is usually associated with the high cost or undesired metal catalytic effects. Recently, there is a growing tendency for using the cost-effective and inert quartz or fused silica glass tubes in hydrothermal experiments. Here, we provide a protocol for carrying out organic-mineral hydrothermal experiments in silica tubes, and we describe the essential steps in the sample preparation, experimental setup, products separation, and quantitative analysis. We also demonstrate an experiment using a model organic compound, nitrobenzene, to show the effect of an iron-containing mineral, magnetite, on its degradation under a specific hydrothermal condition. This technique can be applied to study complex organic-mineral hydrothermal interactions in a relatively simple laboratory system.

Earth-abundant minerals play important roles in the natural hydrothermal systems. Here, we describe a reliable and cost-effective method for the experimental investigation of organic-mineral interactions under hydrothermal conditions.

研究矿物对有机热液转化影响的实验协议

Organic-mineral interactions are widely occurring in hydrothermal environments, such as hot springs, geysers on land, and the hydrothermal vents in the ...

Measuring the Densities of Aqueous Glasses at Cryogenic Temperatures

We demonstrate a method for determining the vitreous phase cryogenic temperature densities of aqueous mixtures, and other samples that require rapid cooling, to prepare the desired cryogenic temperature phase. Microliter to picoliter size drops are cooled by projection into a liquid nitrogen-argon (N2-Ar) mixture. The cryogenic temperature phase of the drop is evaluated using a visual assay that correlates with X-ray diffraction measurements. The density of the liquid N2-Ar mixture is adjusted by adding N2 or Ar until the drop becomes neutrally buoyant. The density of this mixture and thus of the drop is determined using a test mass and Archimedes principle. With appropriate care in drop preparation, management of gas above the liquid cryogen mixture to minimize icing, and regular mixing of the cryogenic mixture to prevent density stratification and phase separation, densities accurate to &#60;0.5% of drops as small as 50 pL can readily be determined. Measurements on aqueous cryoprotectant mixtures provide insight into cryoprotectant action, and provide quantitative data to facilitate thermal contraction matching in biological cryopreservation.

A protocol for determining the vitreous phase densities of micro- to pico-liter size drops of aqueous mixtures at cryogenic temperatures is described.

在低温下测量水性玻璃的密度

We demonstrate a method for determining the vitreous phase cryogenic temperature densities of aqueous mixtures, and other samples that require rapid ...

工程学

Methane Hydrate Crystallization on Sessile Water Droplets

This paper describes a method to form methane hydrate shells on water droplets. In addition, it provides blueprints for a pressure cell rated to 10 MPa working pressure, containing a stage for sessile droplets, a sapphire window for visualization, and temperature and pressure transducers. A pressure pump connected to a methane gas cylinder is used to pressurize the cell to 5 MPa. The cooling system is a 10 gallon (37.85 L) tank containing a 50% ethanol solution cooled via ethylene glycol through copper coils. This setup enables the observation of the temperature change associated with hydrate formation and dissociation during cooling and depressurization, respectively, as well as visualization and photography of the morphologic changes of the droplet. With this method, rapid hydrate shell formation was observed at ~-6 &#176;C to -9 &#176;C. During depressurization, a 0.2 &#176;C to 0.5 &#176;C temperature drop was observed at the pressure/temperature (P/T) stability curve due to exothermic hydrate dissociation, confirmed by visual observation of melting at the start of the temperature drop. The "memory effect" was observed after repressurizing to 5 MPa from 2 MPa. This experimental design allows the monitoring of pressure, temperature, and morphology of the droplet over time, making this a suitable method for testing various additives and substrates on hydrate morphology.

We describe a method to form gas hydrate on sessile water droplets to study the effects of various inhibitors, promoters, and substrates on the hydrate crystal morphology.

甲烷水合物在无柄水滴上的结晶

This paper describes a method to form methane hydrate shells on water droplets. In addition, it provides blueprints for a pressure cell rated to 10 MPa ...

Surface Properties of Synthesized Nanoporous Carbon and Silica Matrices

In this work, we report the synthesis and characterization of ordered nanoporous carbon material (also called ordered mesoporous carbon material [OMC]) with a 4.6 nm pore size, and ordered silica porous matrix, SBA-15, with a 5.3 nm pore size. This work describes the surface properties of nanoporous molecular sieves, their wettability, and the melting behavior of D2O confined in the differently ordered porous materials with similar pore sizes. For this purpose, OMC and SBA-15 with highly ordered nanoporous structures are synthesized via impregnation of the silica matrix by applying a carbon precursor and by the sol-gel method, respectively. The porous structure of investigated systems is characterized by an N2 adsorption-desorption analysis at 77 K. To determine the electrochemical character of the surface of synthesized materials, potentiometric titration measurements are conducted; the obtained results for OMC shows a significant pHpzc shift toward the higher values of pH, relative to SBA-15. This suggests that investigated OMC has surface properties related to oxygen-based functional groups. To describe the surface properties of the materials, the contact angles of liquids penetrating the studied porous beds are also determined. The capillary rise method has confirmed the increased wettability of the silica walls relative to the carbon walls and an influence of the pore roughness on the fluid/wall interactions, which is much more pronounced for silica than for carbon mesopores. We have also studied the melting behavior of D2O confined in OMC and SBA-15 by applying the dielectric method. The results show that the depression of the melting temperature of D2O in the pores of OMC is about 15 K higher relative to the depression of the melting temperature in SBA-15 pores with a comparable 5 nm size. This is caused by the influence of adsorbate/adsorbent interactions of the studied matrices.

Here we report the synthesis and characterization of ordered nanoporous carbon (with a 4.6 nm pore size) and SBA-15 (with a 5.3 nm pore size). The work describes the surface and textural properties of nanoporous molecular sieves, their wettability, and the melting behavior of D2O confined in the materials.

合成纳米碳和二氧化硅矩阵的表面性能

In this work, we report the synthesis and characterization of ordered nanoporous carbon material (also called ordered mesoporous carbon material [OMC]) ...

Studying Surfactant Effects on Hydrate Crystallization at Oil-Water Interfaces Using a Low-Cost Integrated Modular Peltier Device

We introduce an approach to study the formation and growth of hydrates under the influence of nonionic surfactants. The experimental system includes a temperature regulator, visualization techniques, and inner pressure measurements. The temperature control system contains a low-cost, programmable temperature regulator made with solid-state Peltier components. Along with the temperature control system, we incorporated visualization techniques and internal pressure measurements to study hydrate formation and inhibition in the presence of nonionic surfactants. We studied the hydrate-inhibiting ability of nonionic surfactants (sorbitane monolaurate, sorbitane monooleate, PEG-PPG-PEG, and polyoxyethylenesorbitan tristearate) at low (i.e., 0.1 CMC), medium (i.e., CMC), and high (i.e., 10 CMC) concentrations. Two types of crystals were formed: planar and conical. Planar crystals were formed in plain water and low surfactant concentrations. Conical crystals were formed in high surfactant concentrations. The results of the study show that conical crystals are the most effective in terms of hydrate inhibition. Because conical crystals cannot grow past a certain size, the hydrate growth rate as a conical crystal is slower than the hydrate growth rate as planar crystal. Hence, surfactants that force hydrates to form conical crystals are the most efficient. The goal of the protocol is to provide a detailed description of an experimental system that is capable of investigating the cyclopentane hydrate crystallization process on the surface of a water droplet in the presence of surfactant molecules.

We present a protocol to study the formation of hydrates in the presence of nonionic surfactants on the interface of a water droplet submerged in cyclopentane. The protocol consists of building a low-cost, programmable, temperature regulator. The temperature control system is combined with visualization techniques and internal pressure measurements.

使用低成本集成模块化 Peltier 器件研究油水界面水合物结晶的超活性剂效应

We introduce an approach to study the formation and growth of hydrates under the influence of nonionic surfactants. The experimental system includes a ...

Measuring Electrical Conductivity to Study the Formation of Brines Under Martian Conditions

This paper describes a protocol to design experiments to study the formation of brines under Martian conditions and monitor the process with electrical conductivity measurements. We used the Engineering Qualification Model (EQM) of Habitability: Brines, Irradiation, and Temperature (HABIT)/ExoMars 2022 instrument for the experiment setup but we provide a brief account of constructing a simple and inexpensive electrical conductivity measurement setup. The protocol serves to calibrate the electrical conductivity measurements of the salt deliquescence into brine in a simulated Martian environment. The Martian conditions of temperature (-70 &#176;C to 20 &#176;C), relative humidity (0% to 100%) and pressure (7 - 8 mbar) with carbon-dioxide atmosphere were simulated in the SpaceQ Mars simulation chamber, a facility at the Lule&#229; University of Technology, Sweden. The hydrate form of the known amount of salt accommodated between a pair of electrodes and thus the electrical conductivity measured depends predominantly on its water content and the temperature and relative humidity of the system. Electrical conductivity measurements were carried out at 1 Hz while exposing salts to a continuously increasing relative humidity (to force transitioning through various hydrates) at different Martian temperatures. For demonstration, a day-night cycle at Oxia Planum, Mars (the landing site of ExoMars 2022 mission) was recreated.

The objective of the protocol is to monitor the hydration of salts and the brine formation process. Electrical conductivity is used as the measurement technique. The experiments are performed in a simulated Martian environment of temperature, relative humidity and carbon-dioxide atmosphere.

This paper describes a protocol to design experiments to study the formation of brines under Martian conditions and monitor the process with electrical ...

A Microfluidic Approach for the Study of Ice and Clathrate Hydrate Crystallization

An accurate mechanistic description of water crystallization is challenging and requires a few key elements: superb temperature control to allow the formation of single microscopic crystals and a suitable microscopy system coupled to the cold stage. The method described herein adds another important feature that includes exchanging solutions around ice and clathrate hydrate crystals. The described system comprises a combination of unique and home-developed instruments, including microfluidics, high-resolution cold stages, and fluorescence microscopy. The cold stage was designed for microfluidic devices and allows for the formation of micron-sized ice/hydrate crystals inside microfluidic channels and the exchange of solutions around them. The temperature resolution and stability of the cold stage is one millikelvin, which is crucial for controlling the growth of these small crystals. This diverse system is used to study the different processes of ice and hydrate crystallization and the mechanism by which the growth of these crystals is inhibited. The protocol describes how to prepare microfluidic devices, how to grow and control microscopic crystals in the microfluidic channels, and how the utilization of the flow of liquids around ice/hydrate crystals affords new insights into the crystallization of water.

The present protocol describes the crystallization of microscopic ice crystals and clathrate hydrates in microfluidic devices, enabling liquid exchange around the formed crystals. This provides unparalleled possibilities to examine the crystallization process and binding mechanisms of the inhibitors.

一种用于研究冰和包合物水合物结晶的微流控方法

An accurate mechanistic description of water crystallization is challenging and requires a few key elements: superb temperature control to allow the ...