Silicones are an extraordinarily versatile family of products with a striking diversity of applications that make life safer, more pleasant, more exciting and more comfortable. Their flexibility encourages and facilitates innovation and, as silicones are often used to enhance performance, they also help to promote sustainable patterns of resource consumption. Silicones make millions of products perform better, longer and more reliably. Silicones are sophisticated products that are extremely versatile and can be manufactured in more than 2,000 different forms, within the general categories of silanes, fluids, elastomers and resins. Silicones have important chemical and physical qualities derived from their molecular structure. Depending on requirements, these include longevity, thermostability, chemical, electrical and ultraviolet resistance, enduring elasticity, tensile strength, inertness and microbial resistance. They can be formulated either to resist or absorb water. They are much valued for their purity, especially for advanced electrical devices, and for their cleanliness.
有机硅是一个极其丰富多彩的产品家族,具有令人惊奇的多样化应用,使生活更安全,更愉快,更激奋,也更舒适。其灵活多样启迪并促成创新;由于有机硅多用于性能提高,所以还有助于推动可持续的资源消费模式。有机硅使数以百万的产品性能更好,更持久,更可靠。有机硅是极其多用的精巧产品,可以制成2000种以上不同形态,包括常规类别的硅烷,流体,弹性体和树脂等。有机硅具有源于其分子结构的重要化学和物理特性。这些特性,根据需要,可展现为使用寿命,热稳定性,防化,阻电和耐紫外线性,持久的弹性,拉伸强度,化学惰性和抗微生物性等。其可以配制成疏水或吸水材料。其纯度极具价值,尤其对于高级的电气设备,同样,其洁度亦具价值。
有机硅,即有机硅化合物,狭义是指含有Si-C键、且至少有一个有机基是直接与硅原子相连的化合物;习惯上也常把那些通过氧、硫、氮等使有机基与硅原子相连接的化合物也称作有机硅化合物。这样也就扩展到以硅氧键(-Si-O-Si-)为骨架组成的聚硅氧烷,这是有机硅化合物中为数最多,研究最深、应用最广的一类,约占总用量的90%以上。常称的有机硅,聚二甲基硅氧烷,具有奇妙功能的秘密就在于其柔韧的Si-O-Si主链。
• Construction 建筑
Conservation & protection 防水防潮
Sealants 密封
Other 其它
• Electrical & electronics Appliances 电气电子设备
Power, utilities & cables 电力供电线缆
Other 其它
• Industrial 工业
Industrial equipment & moulds 工业设备和模具
Plastics, auxiliaries & chemicals 注塑,助剂和化学品
Other 其它
• Personal & lifestyle 生活时尚
Health & medical care 健康医护
Personal & home care 个人和家居用品
Other 其它
• Special systems 特制品
Adhesives & coatings 黏胶和涂料
Paper 造纸
Textiles & leather 纺织和皮革
Other 其它
• Transportation 交通
Automotive 汽车
General transportation 通用交通
By definition, silicon-hydrogen products (or“SiH products”in short) are silicon products containing Si-H bonds. These products will liberate hydrogen in some circumstances, presenting a major risk of explosion or fire that is proportional to the rate and/or volume of hydrogen released. The silicon-hydrogen products concerned are:
照定义看,硅 - 氢产物(或简称“SiH产物”)是含有Si-H键的硅产物。这些产物在一定情况下会释放氢,产生与氢的释放速率和/或体积成正比的爆炸或火灾的重大风险。相关的硅 - 氢产品包括:
1. Chlorosilanes containing Si-H bonds such as Me2HSiCl, MeHSiCl2, HSiCl3 and others which will readily react with water to form corrosive and toxic hydrogen chloride gas and hydrochloric acid.
含有Si-H键的氯硅烷,如Me 2 HSiCl,MeHSiCl 2,HSiCl 3等,它们容易与水反应形成腐蚀性的毒性氯化氢气体和盐酸。
2. SiH silicone fluids such as Me3Si-O-(Me2Si-O)n-(MeHSi-O)m-SiMe3 and others, generally with a very high SiH content.
SiH硅氧烷液体,例如Me 3 Si-O-(Me 2 Si-O)n - (MeHSi-O)m -SiMe 3等,通常具有非常高的SiH含量。
3. SiH emulsions SiH乳液
and to a certain extend Compounded elastomers generally RTV2, HTV and LSR based on SiH-SiVinyl curing system
以及某种程度上讲,复合弹性体,通常为基于SiH-SiVinyl固化体系的RTV2,HTV和LSR
4. Functionalised silicone fluids for their unreacted residual SiH
用于未反应的残余SiH的 具功能性的硅氧烷液体
There are 16 commonly used chlorosilanes and more that are known and are used in commerce. 氯硅烷有16种常用的,以及其它一些已知,并商用的。
Dimethylchlorosilane (CH3)2HSiCl 二甲基氯硅烷
Trimethylchlorosilane (CH3)3SiCl 三甲基氯硅烷
Methyldichlorosilane CH3HSiCl2 甲基二氯硅烷
Dimethyldichlorosilane (CH3)2SiCl2 二甲基二氯硅烷
Chloropropylmethyldichlorosilane C3H6ClCH3SiCl2 氯丙基甲基二氯硅烷
Vinylmethyldichlorosilane CH2CHCH3SiCl2 二氯甲基乙烯基硅烷
Diphenyldichlorosilane (C6H5)2SiCl2 二苯基二氯硅烷
Phenylethyldichlorosilane C6H5C2 H5SiCl2
Methyltrichlorosilane CH3SiCl3 甲基三氯硅烷
Ethyltrichlorosilane C2H5SiCl3 乙基三氯硅烷
Propyltrichlorosilane C3H7SiCl3 丙基三氯硅甲烷
Chloropropyltrichlorosilane C3H6ClSiCl3 氯丙基三氯硅烷
Vinyltrichlorosilane CH2CHSiCl3 乙烯基三氯硅烷
Phenyltrichlorosilane C6H5SiCl3 苯基三氯硅烷
Trichlorosilane HSiC13 三氯(甲)硅烷
Silicon tetrachloride SiC14 四氯化硅
The chlorosilanes all react with moisture in the air or water to produce hydrogen chloride, the principal reaction product that can cause acute injury to any body tissue contacted. The major acute health risks are potentially severe corrosive burns of the skin, eyes or respiratory tract.
氯硅烷全部与空气或水中的水分反应产生氯化氢,这是可能对所接触的任何身体组织造成急性损伤的主要反应产物。其主要急性健康风险是潜在的严重皮肤,眼睛或呼吸道腐蚀性灼伤。
Except for silicon tetrachloride, all of the chlorosilanes may cause fire hazards. Chlorosilane vapours are heavier than air, and, except for trimethylchlorosilane, the liquids themselves are heavier than water.
除四氯化硅外,所有氯硅烷都可能引起火灾。 氯硅烷蒸气比空气重,并且除了三甲基氯硅烷,液体本身比水重。
All of the chlorosilanes react vigorously with water, producing hydrogen chloride and, in the case of trichlorosilane and methyldichlorosilane, flammable hydrogen gas and hazardous residues. Trimethylchlorosilane will react with water to also produce hexamethyldisiloxane, which is a flammable liquid itself.
所有氯硅烷与水剧烈反应,产生氯化氢,在三氯硅烷和甲基二氯硅烷的情况下,产生易燃氢气和危险残余物。三甲基氯硅烷会与水反应,并产生六甲基二硅氧烷,此产物本身是可燃液体。
The chlorosilanes are non-conductors and, therefore, can accumulate static electrical charges when processed, handled or dispensed.
氯硅烷是非导体,因此,加工,处置或出液时会积聚静电。
THE GASSING TRIANGLE 放气三角
SiH Silicone products are quite stable and not generally considered as hazardous materials, but, under specific conditions, they can generate high volumes of hydrogen gas. Because of its specific physical properties (wide explosive limits, low flammability, ignition energy, etc.) the hydrogen generated by gassing can pose a hazard due to pressure build-up, fire or explosion.
SiH有机硅产品相当稳定,通常不认为是有害物料,但在特定条件下,它们可以产生大量氢气。由于其特定的物理性能(爆炸极限,低可燃性,点火能量等),放气产生的氢气可能由于压力积聚,火灾或爆炸而造成危险。
In order to achieve the gassing phenomenon, three conditions are simultaneously required. These conditions are called “the gassing triangle”.
要发生放气现象,同时需要三个条件。这些条件称为“放气三角”。
1 SiH source SiH源
All chemicals containing a silicon-hydrogen bond can generate hydrogen, and pure polymers or compounded products can be concerned alike.
所有含有硅 - 氢键的化学品都可以产生氢,纯聚合物或化合物亦均属此列。
2 Active hydrogen source活性氢源
All chemicals with an “active hydrogen” can contribute to the gassing phenomenon. The most common is water and can be found in products as an impurity or as an ingredient (emulsion). But other chemicals such as alcohols, amines, acids or alkaline materials used for some processes have the same behaviour and can be a source of “active hydrogen”.
带“活性氢”的所有化学品都有助于放气现象。最常见的是水,并且可以作为杂质或作为成分(乳液)存在于产品中。而其它一些化学品,如醇,胺,酸或碱性物料等,用作某些工艺时,也具有相同的作用,也可以是“活性氢”的来源。
3 Catalyst source
Acids, bases, amines, alkaline or acid salts, metal soaps, products of corrosion and contaminants have a catalytic action on the gassing phenomenon.
The rate of gassing is related to the temperature, acidity and basicity (pH), activity of each component, concentration of the components, their solubility in the system and its viscosity. For example, amines are more active catalysts than alkoxides, which in turn are more active than hydroxides.
酸,碱,胺,碱或酸盐,金属皂(metal soaps),腐蚀和污染产物对放气现象具有催化作用。
放气速率与温度,酸度和碱度(pH),每种组分的活性,组分的浓度,在系统中的溶解度及其粘度有关。例如,胺是比醇盐(alkoxides)更有活性的催化剂,而醇盐又比氢氧化物更具活性。
It is also important to mention that this phenomenon occurs sometimes with an induction time. Studies showed that, varying within the system studied, the reaction can “wait” for some random time and then occur with a quick evolution. This can explain that the gassing of hydrogen is not always easily predicted.
Nevertheless, if any of the above three conditions is missing, the “triangle” is broken and therefore no gassing occurs. However some products may be both the active hydrogen source and the catalyst (see above).
同样重要的是,这种现象有时需要一段诱导时间才发生。研究表明,随观察对象系统各异,反应可以“等待”一段长度随机的时间,然后发生并快速演化。这可以解释放氢过程并不总是容易预测的。
无论如何,上述三个条件任一缺失,“三角”破断,放气即不发生。然而,某些物料可以既是活性氢源,又是催化剂。
Chlorosilanes are stable in the absence of air, moisture and catalytic agents. The catalysts that may cause decomposition and rearrangement include bases; Lewis acids, such as aluminium chloride and iron trichloride; and anhydrous bases, such as Grignard reagents, organoalkali compounds and metal hydrides. When it is necessary to mix hydrochlorosilanes with such reagents, allow for the formation of hydrogen and other gases.
Chlorosilanes, except for silicon tetrachloride, are flammable and can form explosive mixtures with air. Moisture in air causes hydrolysis; hydrogen chloride fumes will be generated.
Water reacts vigorously with chlorosilanes, forming large volumes of hydrogen chloride. Trichlorosilane and methyldichlorosilane reacted with water can also produce hydrogen. Hydrogen can further be generated when hydrochloric acid reacts with some metals.
Primary alcohols react with chlorosilanes almost as rapidly as does water, forming hydrogen chloride; secondary and tertiary alcohols react less rapidly.
Ammonia and the aliphatic amines react rapidly with chlorosilanes, generating heat and solids (ammonium and amine salts).
Bases react violently with chlorosilanes, generating heat and potentially generating hydrogen with hydrogen-containing chlorosilanes.
Chlorine will react violently with any hydrogen-containing chlorosilane.
氯硅烷在没有空气,水分和催化剂的情况下是稳定的。可能引起分解和重组的催化剂包括碱; 路易斯酸,如氯化铝和三氯化铁; 和无水碱,例如格氏试剂,有机碱化合物和金属氢化物。 当需要将氢氯硅烷与这些试剂混合时,要充分考虑氢气和其它气体的产生。
氯硅烷,除四氯化硅外,都是易燃的,可与空气形成爆炸性混合物。空气中的水汽会引起水解; 会产生氯化氢烟雾。
氯硅烷与水会剧烈反应,形成大量氯化氢。三氯硅烷和甲基二氯硅烷与水反应则会产生氢。 而盐酸与一些金属反应时也可进一步产生氢。
氯硅烷与一级醇反应几乎与水一样快,形成氯化氢; 二级醇、三级醇反应较慢。
氯硅烷与氨和脂族胺快速反应,产生热和固体(铵盐和胺盐)。
氯硅烷与碱反应剧烈,产生热量,含氢的氯硅烷与之则可能产生氢。
氯会与任何含氢氯硅烷剧烈反应;就像氧的氧化作用一样。
SPECIFIC DANGEROUS REACTIONS OF SiH PRODUCTS SiH硅烷产品特定的危险反应
It should be pointed out that even in the absence of an active hydrogen source, SiH products themselves may pose additional hazards. Polymerisation, de-polymerisation and equilibration processes can lead to side reactions producing dangerous volatile and highly flammable gases other than hydrogen.
In the presence of acid or basic catalysts (Lewis acids or bases, clays etc.) and - even in the absence of humidity – restructuring of the siloxane chain has been observed in association with the formation of highly flammable, gaseous by-products like for example Me3SiH, Me2SiH2, MeSiH3, depending on the nature of substituents (Me = Methyl, CH3) present on the siloxane backbone.
In extreme cases (H-Siloxane) where tri-functional HSiO1.5 units are present, the formation of SiH4 has been reported. SiH4 is a highly volatile (b.p. –112 °C) and self-ignitable gas on air.
Incompatibility: account should be taken of very severe reactions with peroxides and oxidizers leading to temperature increase and fire.
应当指出,即使在没有活性氢源的情况下,SiH产物本身也可能造成额外的危害。聚合,去聚合和平衡过程可导致副反应,产生氢以外的危险性高度易燃挥发性气体。
在酸或碱性催化剂(路易斯酸或碱,粘土等)存在时,并且 - 即使在没有湿气的情况下 - 观察到硅氧烷链的重构,从而形成高度易燃的气态副产物,例如Me 3 SiH,Me 2 SiH 2,MeSiH 3,这取决于存在于硅氧烷主链上的取代基(Me =甲基,CH 3)的性质。
极端情况下(H-硅氧烷),即存在三官能HSiO1.5 单元时,已有报道能形成SiH 4。 SiH 4是高挥发性(沸点-112℃)和自燃气体。
不相容性:要充分考虑与过氧化物和氧化剂的强烈反应,其可导致温度升高和火灾。
ASSOCIATED HAZARDS 其它危害
As mentioned previously, build-up, fire or explosion can be generated by hydrogen gassing.
Stored in an inappropriate closed container, products can release enough hydrogen to develop a substantial pressure. The sudden release of overpressure can propel any loose part of the container as a dangerous projectile potentially causing serious injuries to people around. That’s why venting devices are needed for storage for “Control of Hazards” and closed glass bottles are not recommended for samples storage.
如前所述,放氢可形成积聚,并引发燃烧或爆炸。
储存在不适当的密闭容器中,物料可释放足够的氢气并产生明显的压力。超压突然释放可以把容器的任何松动部分像危险的弹丸一样飞喷出去,可能严重伤害周边人员。这就是为什么存储需要通风装置作为“危害控制”的原因,不建议将封闭的玻璃瓶用于样品存储。
The release of hydrogen is also hazardous as hydrogen has exploding properties even at low concentrations (explosive limits for hydrogen in air are generally mentioned in literature between 4% and 74%). Exposed to an electric spark, heat or open flame, a hydrogen/air mixture burns with a very hot flame and can be source of bigger fires. All the necessary precautions for the safe handling of flammable gases should, therefore, be observed as mentioned in MSDS.
氢的泄放也很危险,因为氢甚至在低浓度下也具有爆炸性质(文献中通常提及空气中氢的爆炸极限在4%和74%之间)。接触电火花,热源或明火,氢/空气混合物会引燃并散发高热火焰,也是更大火灾的起源。因此,应当遵守MSDS中提及的所有必要的安全处置可燃气体的预防措施。
Sometimes, for viscous products, hydrogen gassing can bring out foaming and overflowing of containers due to build-up.
Reaction of SiH containing products may also form – besides hydrogen gas - solid/resinous products capable to block pipes, exhausts or safety valves which may lead to a rise of pressure in the manufacturing system.
有时,对于粘性产品,由于氢气积聚,可以引起容器内泛泡和溢出。
除了氢气之外,含SiH物料反应还会形成固体/树脂产物,并会阻塞管道,排气或安全阀,从而导致制造系统中的压力升高。
POTENTIAL GASSING PRODUCTS 潜在的放气产品
EMULSIONS Emulsions are the most sensitive potential gassers because they usually contain a fairly high SiH level and have an unlimited supply of active hydrogen in the form of water. So they are therefore very sensitive to catalyst pollution.
乳液是最敏感的潜在放气剂,因为它们通常含有相当高的SiH水平,并且具有以水的形式无限供应的活性氢。因此,它们对催化物污染非常敏感。
COMPOUNDED ELASTOMERS Some RTV, HTV and LSR silicone products contain more SiH compounds. Moisture from fillers, polymerization catalyst residues from polymers and contamination during repackaging may cause reaction and gassing. If viscosity is high, foaming and overflowing could happen.
一些RTV,HTV和LSR有机硅产品含有更多的SiH化合物。源自填料的水分,来自聚合物的聚合催化剂残余物和在分包装期间的污染可能引起反应和放气。如果粘度高,则可能发生泛泡和溢出。
SiH SILICONE FLUIDS Hydrogen siloxane fluids can have a very high SiH content. Used and processed under “clean” conditions, they are quite insensitive to gassing. With no active hydrogen content and catalyst, they are stable products, but it remains imperative that water, acids and bases be excluded.
氢硅氧烷液体可含非常高的SiH含量。在“干净”条件下使用和处置,它们对放气极不敏感。由于没有活性氢含量和催化物,它们是稳定的产物,但仍然必须排除水,酸和碱。
FUNCTIONALISED SILICONE FLUIDS Functionalised silicone fluids can generate gassing problems due to unreacted residual SiH. Depending on process conditions, some active hydrogen products can remain. Specific analysis for catalyst contamination should be done.
官能化硅氧烷液体可能由于未反应的残余SiH而产生放气问题。根据工艺条件,可能有一些活性氢产物保留。应进行催化剂污染的专门分析。
SPECIFIC HAZARDOUS CAUSES 特殊危险的原因
There are many ways in which these conditions can arise as mentioned in the following examples.
有很多方法可以产生这些条件,如下面的例子所提到的。
INADEQUATE EQUIPMENT CLEANOUT
Generally, equipment cleanout includes both solvent and water flushing followed by drying. When inadequate cleanouts occur, trace amounts of catalyst and active hydrogen compounds (water for example) may be left behind completing the gassing triangle for the following batch. Caustic cleaning will cause the same phenomena.
设备清洁不当
通常,设备清洗包括溶剂和水冲洗,然后干燥。洗消不当时,可能留下痕量的催化物和活性氢化合物(例如水),给下一批次反应形成放气三角。苛性清洗会引起相同的现象。
INCOMPLETE PROCESS SEPARATION
If an active hydrogen compound (water, alcohol, amine, etc) is used during the manufacturing process of the SiH fluid or compound, and incompletely separated after, the active hydrogen left behind could later complete the gassing triangle if a catalyst is also present.
工艺分离不完全
如果在SiH液体或化合物的制造过程期间使用活性氢化合物(水,醇,胺等),并且之后分离不完全,则如果还存在催化物,残余活性氢可以随后形成放气三角。
POOR CONTAINER LINERS OR UNPROTECTED STORAGE CONDITIONS
Poor container liners or unprotected storage conditions can cause moisture (water is an active hydrogen source) contamination due to cracking of liners or bad water tightness of venting devices.
不良容器内衬或未经防护的存储条件
不良的容器内衬或未保护的储存条件可能由于内衬开裂或排气装置水密性不良而导致水汽(水是活性氢源)污染。
RUSTING OR POLLUTION OF CONTAINERS
Rusting in containers occurs due to damage such as denting, rupturing, or cracking of container liners, thereby allowing moisture to enter the container and to cause chemical corrosion. The by-products of the corrosion process often have a catalytic action on the gassing phenomenon. Also, accidental introduction of rust or of other contaminants during container filling operations can have the same consequences.
容器腐蚀或污染
容器生锈常由于诸如容器内衬凹陷,破裂或裂纹等各种损伤而产生,从而使水分进入容器并引起化学腐蚀。 腐蚀过程的副产物通常对放气现象有催化作用。此外,在容器灌装操作期间意外引入的锈污或其它污染物可能具有相同的结果。
PRODUCT BREAKDOWN
In some cases, hydrogen evolution may be caused by the chemical breakdown of a product due to ageing. Most products have recommended shelf lives which should be safely observed.
物料分解
在某些情况下,氢析出可能是由于物料久储,化学分解引起的。大多数产品有推荐的保质期,应该安全遵守。
The total equipment, such as lines, pumps, valves, vessels, etc., must be thoroughly dried with no trace of water remaining before introducing any SiH product unless SiH emulsions and dispersions are produced.
除非生产SiH乳液和分散体,导入其它任何SiH产品之前,整体设备例如管线,泵,阀门,容器等,必须彻底干燥,不留任何痕量水分。
Prior to operation, the system should be tested for leaks at or above operating pressure with dry inert gas (nitrogen) and each joint painted with soap solution and checked for bubbles.
在操作之前,应使用干燥的惰性气体(氮气)对系统在操作压力或以上进行检漏,并对每个接头涂上皂液并检看冒泡。
Whenever necessary, totally enclosed systems should be used. Atmospheric openings or vents will allow moisture to enter the system causing the generation of hydrogen under unfavourable conditions and causing the generation of hydrogen chloride (for chlorosilane), which will attack the equipment.
只要有必要,即应使用全封闭系统。大气敞口或通风口将使水分进入系统,导致在不利的条件下产生氢气并导致氯化氢(对氯硅烷而言)的产生,其将侵蚀设备。
Use only dry inert gas (nitrogen), when any of the following must be done: pressurising vessels, priming pumps, blanketing tanks, and filling or withdrawing of tank contents.
必须进行以下任何操作时,只使用干燥的惰性气体(氮气):对容器加压,预注泵,氮封储罐,以及灌装或提取罐物料。
Storage and filtration equipment
All storage tanks for SiH products should be ‘blanketed’ or ‘padded’ with nitrogen. Grounding and bonding must be provided for tanks and ancillary transfer equipment, and when filling drums and IBCs. Free-fall or splash filling of vessels and containers should be avoided by the use of, for example, dip pipes.
High levels of static electricity can be generated when filtering SiH materials. Care should be taken to ensure that effective grounding is in place, and that lines are purged with nitrogen prior to and after filtration, particularly if the equipment is to be subsequently opened up.
储存和过滤设备
SiH产品的所有储罐应采用氮气“氮封”或“填充”。 必须对储罐和辅助输送设备以及在装桶和装IBC时进行接地连接。应通过使用例如浸没管来避免落体式或飞溅式充装槽罐容器。
当过滤SiH材料时会产生高强度静电。应注意确保有效接地,并且在过滤之前和之后,特别是如果随后打开设备时,用氮气吹扫管线。
STATIC ELECTRICITY
Pure SiH fluids show a very low electrical conductivity in general. Thus SiH fluids are extremely prone to accumulation of static electricity.
Static electricity discharges can ignite flammable SiH product vapour. It is therefore essential to inert the whole system in which flammable SiH products or mixtures are present. Dry inert gas (nitrogen) should be used for transfer operations.
纯SiH流体通常显示非常低的电导率。因此,SiH流体非常容易积累静电。
静电放电可点燃易燃SiH物料蒸气。因此,必须将存在易燃SiH物料或混合物的整个系统惰性化。干燥惰性气体(氮气)应该用于输运操作。
Static electricity may be generated when SiH products flow through or are discharged from a pipe or fall freely through space. Splash filling is particularly hazardous and should be avoided. Unless a dip tube is installed, vessels, tanks should be filled from the bottom.
To eliminate static charges and avoid spark discharges, a continuous path from the point of generation to ground must be provided. This is best accomplished by electrically interconnecting (bonding) all vessels, piping and related flanges, and grounding all equipment.
Fill lines should be conductively bonded to provide a path to ground externally.
Ground wiring should be designed to provide reasonable protection against physical wear. Periodic checks of continuity to ground should be made.
SiH物料流过管或从管排出或者自由下落通过空间时可产生静电。飞溅灌料特别危险,应予以避免。除非安装了沉底管,否则容器,储罐应从底部灌注。
为消除静电并避免火花放电,应确保从起电点到大地的连续通路。最好通过电气互连 (绑接) 所有容器,管道和相关法兰,以及接所有设备接地。 灌料管线应导电绑接以便在外部提供接地通路。
接地线应设计能提供合理保护,防止物理磨损。 应定期检查对地的连续导通性。
FIRE HAZARDS
The SiH containing materials cause a particular hazard for fire and explosion, as these have the potential to develop hydrogen. Hydrogen is lighter than air, has a very low Lower Explosion Limit of 4 vol. % in air (the Higher Explosive Limit is 74 vol. %). The hydrogen/air mixture burns with a very hot, non-luminous flame that is extremely difficult to see during the daylight.
Particular SiH products, with a relatively high flashpoint, but sensitive to gassing, can create unexpected fire and explosion hazards, for example SiH containing emulsions.
火灾隐患
含SiH物料具有火灾和爆炸的特殊危险,因为它们具有产生氢的潜力。氢气比空气轻,具有非常低的爆炸极限,爆炸下限4 %体积、爆炸上限为74%体积。氢/空气混合物燃烧,h产生极热无色火焰,在日光下极难看到。
特定SiH物料具有相对高闪点,并对敏于放气;可产生意想不到的火灾和爆炸危险,例如含SiH的乳液。
EXTINGUISHING AGENTS
Due to its reactivity with chlorosilanes, water should NOT be used as an extinguishing agent for chlorosilane fires, except for very small fires. Water can also be used to protect exposures and personnel and on the vapour cloud to disperse and dilute the HCl vapour. (Care should be taken, however, to prevent any over-spray or runoff from contacting the chlorosilane.)
Prevent extinguishing agents from entering a container or vessel that contains chlorosilane. The resulting release of hydrogen chloride vapours may over-pressurise the container or vessel, resulting in a sudden rupture of the container or vessel.
Sodium- and potassium-bicarbonate-based dry chemical fire extinguishers have proven effective to extinguish small chlorosilane fires, except those involving hydrogen-containing chlorosilanes such as trichlorosilane and methyldichlorosilane, where success has been marginal at best. Expect to use much larger quantities of dry chemical than would be required to extinguish a similar hydrocarbon fire. Dry chemical is generally not effective on large fires because an adequate amount of agent cannot be delivered quickly enough. Use of dry chemical on hydrogen-containing chlorosilanes will release hydrogen, which may ignite explosively.
灭火剂
水由于与氯硅烷具有反应性,不可用作氯硅烷火灾的灭火剂,除非是非常小的火灾。水倒可以用于隔绝接触,保护人员并在蒸气雾上分散和稀释HCl挥发物。(但应注意防止任何过度喷洒或径流接触氯硅烷。)
要防止灭火剂进入含有氯硅烷的容器或储罐。其所产生的氯化氢蒸气泄放可能使容器或储罐过压,导致容器或储罐突然破裂。已经证明基于碳酸氢钠和碳酸氢钾的干化学灭火器对于扑灭小的氯硅烷火焰是有效的,而对含氢的氯硅烷例如三氯硅烷和甲基二氯硅烷,则成功很少。要预备使用比扑灭类似的烃类火灾所需更大量的干化学品。干燥化学品通常对大面燃烧不起作用,因为够量的药剂却不能尽快地投送。在含氢氯硅烷上使用干燥化学品会释放氢气,可能引发爆炸。
Foam is the most effective agent overall for use on chlorosilane fires. However, a number of variables, most notably the chlorosilane involved, the foam concentrate, the concentration of the foam, the expansion ratio (final foam volume versus initial solution volume), the application equipment and the fire conditions, can have a significant impact on the effectiveness of foam on chlorosilane fires. Certain combinations of these variables can in fact produce less than satisfactory (and even adverse) results.
In general, though, alcohol-(polar) compatible AFFF (Aqueous Film Forming Foam) has proven to be an extremely effective foam type, and medium-expansion foam has been found to be the most effective foam expansion. Other foam types and expansions, however, can produce satisfactory results, especially on fires involving dimethyldichlorosilane, trimethylchlorosilane and other heavily organic substituted chlorosilanes. For chlorosilanes containing Si-H (silicon-hydrogen) bonds, e.g., trichlorosilane and methyldichlorosilane, alcohol-compatible AFFF and medium-expansion foam are highly recommended for maximum effectiveness.
泡沫是用于氯硅烷火灾的最有效的灭火剂。然而,各种变量,包括最要注意的所涉及的氯硅烷,泡沫浓缩物,泡沫的浓度,膨胀比(最终泡沫体积与初始溶液体积),施用设备和火灾条件,可以显著影响泡沫对氯硅烷火灾的有效性。这些变量的某些组合实际上可能产生不令人满意的(甚至不利的)结果。
然而,总体而言,醇 – (极性)相容的AFFF(水性成膜泡沫)已证明是非常有效的泡沫类型,而中度膨胀泡沫已发现是最有效的泡沫膨胀物。当然其它一些泡沫类型和膨胀物也可得到令人满意的结果,特别是在涉及二甲基二氯硅烷,三甲基氯硅烷和其它重有机化氯硅烷燃烧方面。 对于含有Si-H(硅 - 氢)键的氯硅烷,例如三氯硅烷和甲基二氯硅烷,强烈建议使用醇容性AFFF和中度膨胀泡沫以达到最佳效果。
Since foam solutions contain water, reaction with the chlorosilane will normally be observed when foam is applied. Be aware that application of foam will release significant amounts of corrosive vapours. In addition, hydrogen vapours can he released from hydrogen-containing chlorosilanes and may be trapped under the foam blanket. Extreme care should be taken not to disturb the foam blanket during and after foam application.
Other extinguishing agents that may be effective on small fires include dry sand and carbon dioxide. (Caution: When using carbon dioxide in enclosed spaces without adequate ventilation, an asphyxiation hazard can be created.)
泡沫溶液含水,使用泡沫时通常观察到其与氯硅烷的反应。请注意,施用泡沫会释放大量的腐蚀性蒸气。 此外,氢气可以从含氢的氯硅烷释放并且可以被封堵在泡沫覆盖层下。泡沫施用期间和之后,应当非常小心不要扰动泡沫层。
对小型燃烧有效的其他灭火剂包括干砂和二氧化碳。(注意:在没有足够通风的密闭空间中使用二氧化碳时,可能会产生窒息危险。)