CN86102290B - 水合硅酸钙材料及其制备方法和用途 - Google Patents
水合硅酸钙材料及其制备方法和用途 Download PDFInfo
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Abstract
一种基于水合硅酸钙、包含主要成分为１１Ａ雪硅钙石纤维、其中可任意地掺入少量的无机和／或有机纤维的新材料，它的湿法制备方法以及此材料在恶劣条件下，需要有非常好的全面绝缘性能和适宜机械强度的技术领域中的应用。
Description
本发明涉及具有隔热性、电绝缘性、隔声和减振作用，并具有高机械强度和持久耐水性及耐二氧化碳性的以水合硅酸钙（Ca-hydrosilicate）为基料的新材料;它的新制备方法及在那些需要用具有良好的通用绝缘性能而又同时具有适当的机械强度和高温稳定性的新材料的科技领域内的应用。
联邦德国专利申请说明书DE-A-914265公开了一种具有耐热性和电绝缘性能的材料的制备方法，其中水合原料如水合硅酸镁，与一种或多种还原金属混合，然后加热以除去水合的水;该混合物也可含有高达2%的碱金属或碱土金属的硝酸盐。
可含有纤维的水合硅酸钙的绝热材料已为人们所熟知。然而，迄今为止它们均不能令人满意，例如在热聚集的情况下或恶劣条件下使用时，不是缺乏机械强度（特别是暴露在高温时）就是丧失其绝缘性能，甚至两者兼差;由于它们的热稳定性、耐水性等均已下降、它们的工作寿命也相应缩短。市场上销售的水合硅酸钙材料，在暴露于1273.15°K高温后，其抗压缩性为49N/cm2。
因此，它们的应用范围是特定的，也是相当狭窄的。在现有技术中，寻找一种具有良好的绝缘性能、同时也具有良好的机械强度和热稳定性的通用材料的问题尚未得到解决。
现在已发现一种水合硅酸钙的材料，其中含有主要成分为11
的雪硅钙石（tobermorite）纤维，并可任意地掺入少量的无机和/或有机纤维，这种材料即使在恶劣条件下也具有优良的隔热性、电绝缘性、隔声和减振作用，持久耐二氧化碳和耐水的性能，同时又有很高的机械强度。当此材料含有按质量百分比为80%的具有良好结晶结构的11
雪硅钙石纤维时，其各种性能均属优良。
具有非显而易见的特性的上述材料是本发明的主要目的。
本发明的另一目的是根据下列化学式，制备含有主要成分为11
的雪硅钙石纤维的水合硅酸钙材料的新方法：
5Ca（OH）2+6SiO2+5.5H2O+q（J）→
5CaO×6SiO2×10.5H2O
用所谓“湿”法，相应地从溶液和悬浮液开始。而至今已知的合成法是在湿模块或其他成型块的情况下进行的。
本发明所述的方法如下：熟石灰和粒子尺寸最大为93微米的石英粉（SiO2含量的质量百分比至少为80%），在熟石灰和二氧化硅之比为0.73至0.76的情况下，相继加入质量百分比为0.3至1.5%的羧甲基纤维素碱性盐的水溶液中。在此悬浮液中，加入按质量百分比（以悬浮液中的固相计算）为5至8%的无机或有机纤维（最大长度为10mm），使悬浮液中固相与液相之间的比例大约为4.5至5.5的范围。再将所述悬浮液装入模具中，使它在12至16小时内经受7.0至11.0巴的水蒸气的作用，产品从模具中取出来后，在最高温度为493°K下干燥。
羧甲基纤维素的碱性盐以羧甲基纤维素钠为好;所用无机纤维是用10毫米长的石棉纤维，而有机纤维则以10毫米长的亚麻，大麻或黄麻纤维为好。
必须指出，所述的纤维并非为增强水合硅酸钙的结构而加入去的;而是作为添加物诱导结晶作用以便生成具有所需良好结晶结构的纤维状的11
雪硅钙石。在不受任何理论限制的情况下，本发明人认为，它们是在合成反应中起阻滞剂的作用，因而使11
雪硅钙石的选择性结晶得以进行。对产品的X射线衍射分析证实了高含量的11
雪硅钙石良好结晶的存在。
当11雪硅钙石良好结晶形成之后，上述纤维的存在已成为无关紧要的了，当该材料继续升温，而达到高温时，它们将被破坏。
新材料的性质很明显，具有大体上整体均相结构的特征。与此相反，先有技术中的材料则在升温时，分解成它们原来的成分。
基于它的结构和构成的新特征，本发明要求保护的材料不论是在静态或动态，热聚集或其他聚集形式的条件下，均是一种用途广的材料。
本发明的另一目的，是此种水合硅酸钙的含有主要成分为11
雪硅钙石纤维的材料，作为具有隔热性、电绝缘性、隔声和减振作用、同时有高机械强度及持久耐水性和耐二氧化碳性的材料的应用，熟悉此技术的人员可设想其用途。
下述实例可说明本发明，但在任何情况下不可视为对本发明之限制。
实例1
将熟石灰（300公斤，氧化钙含量的质量百分比为〈＆＆〉加到含有羧甲基纤维素钠（3公斤）和水（1.5立方米）的预混物中，而在其中加入石英粉（300公斤，二氧化硅的含量按质量百分比为〈＆＆〉粒子尺寸小于93微米）。将所获得的溶液加入预先已混合好的湿石棉纤维（38公斤，平均长度约10毫米）和水（12.3立方米），进行搅拌以使所有组分充分混合，并装入模具（内尺寸：1.2米×0.6米×0.3米）中。已装料的模具放在高压釜中进行14小时水热处理，压强在9.18至10.2巴之间。水热处理完毕后，获得白色的块料，干燥并测试之。
实例2
将熟石灰（465.65公斤，氧化钙含量质量百分比为72%）加到羧甲基纤维素钠的水溶液（2000升）中。在其中再加入石英粉（463.5公斤，二氧化硅含量按质量百分比为97.5%，粒子尺寸小于93微米）。搅拌此组合物，并将均匀混合的悬浮液输送到第二个含有水（2200升）或纤维（19公斤亚麻纤维，长度为10-12毫米，和48.5公斤温石棉纤维，长约10毫米）混合液中。搅拌以使各组分均匀混合，将获得的浆状悬浮液装入实例1所述的模具中。
已装料的模具放置在高压釜中，并按下述的温度控制程序进行水热处理：
1.预热：2.5小时（直至9.5巴）
2.等压阶段：11小时，9.5至10巴之间
3.冷却：3小时
经水热处理后由模具中取出的块料总体积为3.65立方米，其无水物含量按质量百分比为79%。并在约为448°K温度下干燥20小时。
测试结果如下：
按实例1和2所制成的块料的性质。
堆积密度：220-280kg/m3
抗压缩性：1，470，900-1，961，200N/m2
抗弯强度：980，600-1，000，000N/m2
总孔隙率：75-85%
经24小时加热，在平均温度为1273.15°K的条下
线收缩率为1.8-2%
表观热导率（在平均温度下）：
473.15°K 0.06978W/mK
573.15°K 0.0872W/mK
673.15°K 0.09769W/mK
上述测试是根据下述标准进行的：
美国材料试验标准（ASTM）C165（压缩性）
美国材料试验标准C203（抗弯强度）
美国材料试验标准C303（密度）
美国材料试验标准C356（线收缩率）
美国材料试验标准C518（热传导）
美国材料试验标准（水和水银）耐火材料（多孔性）的孔隙率测定法
标准试验 南斯拉夫国家标准 U.J.1，040，第7项（燃烧试验）
试验样品不可燃烧;
标准试验 南斯拉夫国家标准 U.J.1，060，第7项（可燃性试验）
试验样品不易燃烧;归入第1类材料。
根据砌砖工程（Brickwork）的隔声条件和技术测量条例来评价（南斯拉夫政府公报（Official Gazette of Yugoslavia），No.35/70）：
厚度为5厘米的试验墙板的隔声能力为28分贝。平均偏差：1分贝。声透射衰减平均值：32分贝
振动阻尼（减振）性能是本发明的材料的一个特征性能，这是基于水合硅酸钙的隔热材料的新优点。
新发明的材料有耐湿性，能吸收湿气直至达到干空气状态。它在水中有持久稳定性，在达到饱和之前不会渗漏水份。它吸收水份的量可超过它原质量的5倍。因此这种材料可在某种情况下作隔水之用。即使在湿态时，它亦有耐冻结作用。
经再干燥后，这种材料仍显示其原有的特性：其抗扩散系数（通过一层本发明材料的水蒸气的传透量除以通过同等厚度的一层气体的水蒸气的传透量）测定结果为μ＝17.8。
这种新材料有抗二氧化碳的性能，并对诸如啮齿类和昆虫等害虫也有抗害功能。
本发明要求保护的材料是白色，甚至是很美丽的有光泽的白色。它也适用于苛刻的场合（建筑工程，食品工艺等）。
工艺方面：这种材料可用例如木工用的工具来加工。其形状可在制备材料时预制，特别是当所需要的形状不能用切割或拉锯而获得或最后产品要求完全或主要部分是原装的、未经机械加工的表面时，尤其需要事先预制。
制件的表面可加以整饰，例如用传统的方法进行油漆。
有理由得出结论，这种新发明材料在各种技术领域内都有广阔的用途的。
因此，凡由本发明说明书介绍的新材料制成的各种物件、元件或部件均属本发明要求保护的对象。在所有技术领域中，凡要求具有全面的绝缘性能且同时具有良好的高稳定性，也具有抗压、防火、防震、防水蒸汽、防二氧化碳等性能的技术领域中，均可用本发明的新材料。
在这方面技术熟练的人员不需经过创造性的努力就会发现，在不限制应用方式的情况下，预期本发明的材料在下列各技术领域中是可应用的：耐火材料、电的或热的绝缘体、发电站设备、建筑工程（特别在恶劣气候条件下）、家具、金属结构的防护、贮水器、冰箱、冷凝器（如化工中用的）、飞机另件及造船元件等。可引起重视的一个有趣应用是用作催化剂的载体。
Claims (18)
1、一种具有隔热性、电绝缘性、隔声和减振作用，并且有高机械强度和持久耐水性及耐二氧化碳性的水合硅酸钙材料，其特征在于，该水合硅酸钙主要包含按质量百分比计的含量至少为80%的11
雪硅钙石纤维，其中可任意掺入少量的无机和/或有机纤维。
2、权利要求1所述材料，其特征在于该材料具有下列特性（美国材料试验标准）：
堆积密度：220-280kg/m3
抗压缩性：1，470，900-1，961，200N/m2
抗弯强度：980，600-1，000，000N/m2
总孔隙率：75-85%
经24小时加热，在平均温度为127315K的条下线收缩率为1.8-2%表观热导率（在平均温度下）：
473.15°K 0.06978W/mK
573.15°K 0.0872W/mK
673.15°K 0.09769W/mK
3、权利要求1所述材料，其特征在于，该无机纤维是长度约为10毫米的石棉纤维。
4、权利要求1所述材料，其特征在于，该有机纤维是亚麻，大麻或黄麻纤维，其长度约为10毫米。
5、制备具有隔热性、电绝缘性、隔声和减振作用、并具有高机械强度和持久耐水性及耐二氧化碳性的水合硅酸钙材料的方法，其特征在于，将熟石灰和颗粒尺寸最大为93微米且二氧化硅含量至少为质量百分比80%的石英粉，以熟石灰与二氧化硅比例为0.73至0.76，相继加入含有质量百分比为0.3至1.5%的羧甲基纤维素的碱性盐水溶液中。在此悬浮液中，再加入（按固相部分计算）质量百分比为5%至8%的无机或有机纤维，其最大长度约为10毫米，以使悬浮液中固相与液相之比例约在4.5至5.5间的范围内，将所述悬浮液装入模具中，在7.0至11.0巴的压强下，使它受水蒸气作用12至16小时，最后，将产品从模具中取出，在最高温度为493°K干燥。
6、权利要求5所述方法，其特征在于，该无机纤维是长约10毫米的石棉纤维。
7、权利要求5所述方法，其特征在于，该有机纤维是长约10毫米的亚麻、大麻或黄麻纤维。
8、制品，其特征在于，它包含权利要求1至4中任何一项所述的材料。
9、制品，其特征在于，它包含按权利要求5至7中任何一项所述的方法制备的材料。
10、权利要求8或9所述制品的应用，例如耐火材料、电和热的绝缘体、发电站设备，建筑工程零件、家具、金属结构的保护，贮水器，冰箱、化工用冷凝器、飞机零件和造船零件、催化剂载体以及需要非常好的全面绝缘性能和适当机械强度的类似制品。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| YUP553/85 | 1985-04-03 | ||
| YU553/85A YU44495B (en) | 1985-04-03 | 1985-04-03 | Process for making high temperature resistant thermoisolation material |
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| Publication Number | Publication Date |
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| CN86102290A CN86102290A (zh) | 1986-11-12 |
| CN86102290B true CN86102290B (zh) | 1988-11-23 |
Family
ID=25550431
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| Application Number | Title | Priority Date | Filing Date |
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| CN86102290A Expired CN86102290B (zh) | 1985-04-03 | 1986-04-03 | 水合硅酸钙材料及其制备方法和用途 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4873141A (zh) |
| EP (1) | EP0220219B1 (zh) |
| JP (1) | JPS62501595A (zh) |
| KR (1) | KR910001030B1 (zh) |
| CN (1) | CN86102290B (zh) |
| AT (1) | ATE45240T1 (zh) |
| AU (1) | AU5814486A (zh) |
| DE (1) | DE3664831D1 (zh) |
| HU (1) | HUT43982A (zh) |
| IL (1) | IL78411A (zh) |
| WO (1) | WO1986005918A1 (zh) |
| YU (1) | YU44495B (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5240501A (en) * | 1989-06-23 | 1993-08-31 | Vidosava Popovic | Material for heat and electrical insulation with a capacity of selective absorption of electromagnetic radiation spectrum and vibration, its production process and use |
| YU47637B (sh) | 1989-06-23 | 1995-12-04 | Vidosava Popović | MATERIJAL NA BAZI Ca-HIDROSILIKATA ZA TERMO I ELEKTRO IZOLACIJU SA SPOSOBNOŠĆU SELEKTIVNE APSORPCIJE ELEKTROMAGNETNOG SPEKTRA ZRAČENJA I VIBRACIJA I POSTUPAK ZA NJEGOVU PROIZVODNJU |
| CN1045764C (zh) * | 1991-08-09 | 1999-10-20 | 秩父小野田株式会社 | 高强度硅酸钙成形体及其制造方法 |
| DE4339137A1 (de) * | 1993-06-08 | 1994-12-15 | Sicowa Verfahrenstech | Verfahren zur Herstellung von Wärmedämmaterial |
| DE102007027653A1 (de) | 2007-06-15 | 2008-12-18 | Horst Puckelwaldt | Keramische Brandschutzplatte und Verfahren zu deren Herstellung |
| CN104743977B (zh) * | 2015-03-12 | 2016-01-13 | 江苏科技大学 | 一种用于船舶舱壁的防火绝热材料及其制备方法和应用 |
| PL425837A1 (pl) | 2018-06-07 | 2019-12-16 | Ad Alio Spółka Z Ograniczoną Odpowiedzialnością | Sposób wytwarzania powłok oraz mas termorefleksyjnych i termoizolacyjnych |
Family Cites Families (9)
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|---|---|---|---|---|
| DE914265C (de) * | 1939-10-19 | 1954-06-28 | Aeg | Verfahren zur Herstellung von hitzebestaendigen, elektrisch isolierenden Werkstoffen |
| AU409898B2 (en) * | 1965-11-18 | 1971-01-29 | The Colonial Sugar Refining Company Limited | Improvements relating tothe manufacture of calcium silicate hydrate products |
| US3501324A (en) * | 1966-07-15 | 1970-03-17 | Osaka Packing | Manufacturing aqueous slurry of hydrous calcium silicate and products thereof |
| US3902913A (en) * | 1972-04-28 | 1975-09-02 | Owens Corning Fiberglass Corp | Hydrous calcium silicate insulation products |
| US3968072A (en) * | 1972-05-22 | 1976-07-06 | Johns-Manville Corporation | Asbestos fiber and organic polymeric binder heat reaction products and method of forming same |
| US4128434A (en) * | 1976-09-17 | 1978-12-05 | Johns-Manville Corporation | High density asbestos-free tobermorite thermal insulation containing wollastonite |
| GB1553493A (en) * | 1976-11-18 | 1979-09-26 | Mitsubishi Chem Ind | Process for preparing calcuim silicate shaped product |
| US4131638A (en) * | 1977-07-05 | 1978-12-26 | Johns-Manville Corporation | Process for the manufacture of calcium silicate hydrate objects |
| JPS5756316A (en) * | 1980-09-15 | 1982-04-03 | Kubota Ltd | Manufacture of tobermorite |
-
1985
- 1985-04-03 YU YU553/85A patent/YU44495B/xx unknown
-
1986
- 1986-04-02 JP JP61502461A patent/JPS62501595A/ja active Pending
- 1986-04-02 EP EP86902395A patent/EP0220219B1/en not_active Expired
- 1986-04-02 AT AT86902395T patent/ATE45240T1/de not_active IP Right Cessation
- 1986-04-02 HU HU863127A patent/HUT43982A/hu unknown
- 1986-04-02 WO PCT/EP1986/000202 patent/WO1986005918A1/en active IP Right Grant
- 1986-04-02 AU AU58144/86A patent/AU5814486A/en not_active Abandoned
- 1986-04-02 DE DE8686902395T patent/DE3664831D1/de not_active Expired
- 1986-04-02 US US06/847,200 patent/US4873141A/en not_active Expired - Fee Related
- 1986-04-03 IL IL78411A patent/IL78411A/xx unknown
- 1986-04-03 CN CN86102290A patent/CN86102290B/zh not_active Expired
- 1986-12-03 KR KR8670862A patent/KR910001030B1/ko active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| EP0220219A1 (en) | 1987-05-06 |
| DE3664831D1 (en) | 1989-09-07 |
| HUT43982A (en) | 1988-01-28 |
| CN86102290A (zh) | 1986-11-12 |
| WO1986005918A1 (en) | 1986-10-09 |
| JPS62501595A (ja) | 1987-06-25 |
| AU5814486A (en) | 1986-10-23 |
| YU55385A (en) | 1986-12-31 |
| KR910001030B1 (en) | 1991-02-19 |
| IL78411A (en) | 1991-03-10 |
| KR880700434A (ko) | 1988-03-15 |
| ATE45240T1 (de) | 1989-08-15 |
| YU44495B (en) | 1990-08-31 |
| EP0220219B1 (en) | 1989-08-02 |
| US4873141A (en) | 1989-10-10 |
| IL78411A0 (en) | 1986-08-31 |
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