TWI642729B - Densifying agent - Google Patents
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Abstract
一種用於提高碳基材料密度的增密劑，以重量組份為100份，增密劑包含：重量組份為19~30的甲苯不溶物、重量組份為0.1~0.3的喹啉不溶物、重量組份為0~0.001的灰分、重量組份為18~30的喹啉可溶物，其中，精製瀝青的軟化點溫度介於120~140℃之間，藉此，由於增密劑具有較多量的甲苯不溶物及少量的喹啉不溶物可以在與碳基材料混合時，提高碳基材料的密度，並藉由喹啉可溶物的含量來調節含有黏結劑的增密劑的黏結效果。A densifying agent for increasing the density of a carbon-based material, comprising 100 parts by weight, the densifier comprises: a toluene-insoluble matter having a weight component of 19 to 30, and a quinoline insoluble matter having a weight component of 0.1 to 0.3 The ash component having a weight component of 0 to 0.001 and the quinoline soluble matter having a weight component of 18 to 30, wherein the softening point temperature of the refined asphalt is between 120 and 140 ° C, whereby the densifying agent has A larger amount of toluene insoluble matter and a small amount of quinoline insoluble matter can increase the density of the carbon-based material when mixed with the carbon-based material, and adjust the adhesion of the densifier containing the binder by the content of the quinoline soluble matter. effect.
Description
本發明提供一種增密劑，特別的是有關於一種以精製瀝青為主要成份做為提高碳基材料密度的增密劑。The present invention provides a densifier, and more particularly to a densifier which uses refined asphalt as a main component to increase the density of a carbon-based material.
高性能碳基材料(carbon-based materials)由於其具有優良的導電及導熱性能、高溫力學性能及化學穩定性，使，高性能碳基材料愈來愈被人們所重視，並將其用作功能性材料和結構材料，而廣泛地應用於電工電子、冶金、機械、化工、核能、軍事及航太等工業，乃至於家用電器、體育和醫療器材等。High-performance carbon-based materials have become more and more important because of their excellent electrical and thermal conductivity, high-temperature mechanical properties and chemical stability, and they are used as functions. Sex materials and structural materials, and are widely used in electrical and electronic, metallurgy, machinery, chemical, nuclear, military and aerospace industries, as well as household appliances, sports and medical equipment.
高性能碳基材料，如：碳/碳複合材料或工業級石墨材料，其取得的方式通常是藉由黏結劑(binder)混合所需的填料(filler)後加入石墨基材(matrix)中，經擠壓或模制壓縮成型，成型後會再經過高溫碳化等熱處理過程，但在熱處理過程中，由於石墨基材與填料的收縮率不同，會使其產生裂縫與空孔，而縫隙與空孔會造成碳材料的密度及機械強度下降、導熱性變差，因此，經擠壓或模制壓縮成型的碳基材料需再經過多次浸漬增密劑(thickening agent)的增密處理，例如:處理溫度大於等於600℃，處理壓力大於等於12000 psi，來將其縫隙與空孔填滿，以提高碳基材料的密度，如此才能獲得符合需求的高性能碳基材料。High-performance carbon-based materials, such as carbon/carbon composites or industrial grade graphite materials, are usually obtained by mixing the required fillers with a binder and then adding them to a graphite matrix. After extrusion or molding compression molding, it will be subjected to high-temperature carbonization and other heat treatment processes, but in the heat treatment process, due to the different shrinkage ratio of the graphite substrate and the filler, cracks and voids will be generated, and the gaps and voids will occur. The pores cause a decrease in the density and mechanical strength of the carbon material, and the thermal conductivity is deteriorated. Therefore, the carbon-based material which is extruded or molded into a compression molding needs to be subjected to a densification treatment of a plurality of impregnation agents, for example, : The processing temperature is greater than or equal to 600 ° C, and the processing pressure is greater than or equal to 12,000 psi to fill the gaps and voids to increase the density of the carbon-based material, so as to obtain high-performance carbon-based materials that meet the demand.
現有技術中的黏結劑或增密劑多為瀝青(pitch)組成物，包括：石油瀝青(petroleum pitch)、焦煤瀝青(coke pitch)或其組合，瀝青為一種熱塑性高分子，為具有數百種芳香族碳氫化合物的混合物，其中包含3~8個芳香環的多環化合物，常溫下是玻璃相的黑色固體。而瀝青通常是藉由對於不同溶劑的溶解程度，來區別分子量不同的成分。而成分的含量或比例會影響瀝青的軟化點(softening point, SP)、黏度、高溫流動性(滲透微孔能力)及結焦值(coking value, CV)等特性，而這些特性也直接反映在黏結劑或增密劑的應用。Most of the prior art binders or densifiers are pitch compositions, including: petroleum pitch, coke pitch or a combination thereof. Asphalt is a thermoplastic polymer having hundreds of kinds. A mixture of aromatic hydrocarbons comprising a polycyclic compound of 3 to 8 aromatic rings, a black solid which is a glass phase at normal temperature. Bitumen usually distinguishes components with different molecular weights by the degree of dissolution for different solvents. The content or proportion of the ingredients will affect the softening point (SP), viscosity, high temperature fluidity (permeability of microporous) and coking value (CV) of the asphalt, and these characteristics are also directly reflected in the bonding. Application of agent or densifier.
如圖1所示，圖1為瀝青組份的示意圖，瀝青C1可以使用不同極性的溶劑溶解出不同分子量範圍的瀝青，以利於區分瀝青C1內分子量分布與大小。首先，瀝青C1由甲苯溶劑(toulene)區分出甲苯不溶物 C11 (toluene insolubles, TI)及甲苯可溶物 C12 (toluene solubles,TS)，亦稱γ樹脂 ，其中，甲苯可溶物C12的分子量介於200~1000 Dalton之間；而對甲苯不溶物C11則再進一步以喹啉溶劑(quinoline solvent)區分出喹啉不溶物C111 (quinoline insolubles, QI)，亦稱α樹脂及喹啉可溶物 C112 (quinolone solubles, QS)，亦稱β樹脂 ，其中，喹啉不溶物C111的分子量大於1800 Dalton及喹啉可溶物C112的分子量介於1000~1800 Dalton 之間。瀝青內的β樹脂(即喹啉可溶物QS)代表著瀝青本身黏結的能力，因此高品質瀝青的β樹脂的含量是愈高愈好。As shown in Fig. 1, Fig. 1 is a schematic view of a bitumen component. Asphalt C1 can dissolve pitches of different molecular weight ranges using solvents of different polarities to facilitate differentiation of molecular weight distribution and size in pitch C1. First, the pitch C1 distinguishes toluene insolubles (TI) and toluene solubles (TS) from toulene, also known as γ resin, wherein the molecular weight of the toluene soluble material C12 is Between 200 and 1000 Dalton; and the toluene-insoluble C11 further distinguishes quinoline insolubles (QI) with quinoline solvent, also known as alpha resin and quinoline solubles C112. (quinolone solubles, QS), also known as beta resin, wherein the quinoline insoluble C111 has a molecular weight greater than 1800 Dalton and the quinoline soluble C112 has a molecular weight between 1000 and 1800 Dalton. The beta resin (i.e., quinoline solubles QS) in the asphalt represents the ability of the asphalt itself to bond, so the higher the content of the beta resin of the high quality asphalt, the better.
甲苯可溶物(TS)的C/H比約介於0.56~1.25，其主要作用為降低瀝青的黏度，提高塑性，但若含量過多時，會影響瀝青的結焦值，若以此作為黏結劑或增密劑時，甲苯可溶物(TS)就會在增密步驟時以氣體形式逸出，反而無法有效填補碳基材料中的裂縫與空孔，進而影響了碳基材料的密度與機械強度；甲苯不溶物(TI)的C/H比約為1.53，可作為黏結劑成分，所含的喹啉不溶物(QI)的C/H比大於1.67，喹啉不溶物(QI)包含原生喹啉不溶物和次生喹啉不溶物，原生喹啉不溶物來自於原始油料中，包含無機雜質和大分子的芳香烴，次生喹啉不溶物則是在瀝青焦化過程中，由原生喹啉不溶物以外的其他物質縮聚而成，由於喹啉不溶物(QI)並無浸潤與黏結的能力，雖然適量的次生喹啉不溶物可提高黏結劑的結焦值，但過量往往會降低瀝青的黏結特性，並阻塞碳基材料中的氣孔，而影響黏結劑的浸漬效果；而甲苯不溶物 (TI)所含的喹啉可溶物(QS)的C/H比約介於1.25~2.0，喹啉可溶物(QS)為黏結劑提供黏結作用的主要成分，當含量越多時，可有效地提升碳基材料的電阻率、熱導率及機械強度等物化性能。The C/H ratio of toluene solubles (TS) is about 0.56~1.25. Its main function is to reduce the viscosity of asphalt and improve the plasticity. However, if the content is too much, it will affect the coking value of asphalt, and if it is used as a binder. Or a densifier, the toluene solubles (TS) will escape as a gas during the densification step, but will not effectively fill the cracks and pores in the carbon-based material, thereby affecting the density and mechanical properties of the carbon-based material. Strength; toluene insolubles (TI) has a C/H ratio of about 1.53, which can be used as a binder component. The C/H ratio of quinoline insolubles (QI) is greater than 1.67, and quinoline insolubles (QI) contain native Quinoline insolubles and secondary quinoline insolubles, the primary quinoline insolubles are derived from the original oil, containing inorganic impurities and macromolecular aromatic hydrocarbons, and the secondary quinoline insolubles are in the process of asphalt coking, from primary quinolin Polycondensation of other substances other than phenyl insolubles, because quinoline insolubles (QI) have no ability to infiltrate and bond, although an appropriate amount of secondary quinoline insolubles can increase the coking value of the binder, but excessive excess tends to reduce asphalt Bonding properties and block the pores in the carbon-based material The impregnation effect of the binder; while the C/H ratio of the quinoline solubles (QS) contained in the toluene insolubles (TI) is about 1.25-2.0, and the quinoline solubles (QS) provide the bonding agent for the bonding agent. The main component, when the content is more, can effectively improve the physical properties such as electrical resistivity, thermal conductivity and mechanical strength of carbon-based materials.
將瀝青進行精製處理是一種現有的技術手段，例如將原本殘留在瀝青內的喹啉不溶物(QI)去除到低QI的精製瀝青、降低加熱攪拌處理後的瀝青的軟化點或是調整瀝青本身的分子量比例，藉此以達到高品質碳材料並符合工業使用標準。另外，在高壓熱處理過程中，藉由通入氣體的手段來控制瀝青的縮聚的程度與組成以達到精製的目的。The purification of the asphalt is a prior art technique, for example, removing the quinoline insoluble matter (QI) originally remaining in the asphalt to the refined pitch of the low QI, reducing the softening point of the pitch after the heating and stirring treatment, or adjusting the asphalt itself. The molecular weight ratio is used to achieve high quality carbon materials and meet industrial use standards. In addition, in the high-pressure heat treatment process, the degree and composition of the polycondensation of the pitch are controlled by means of introducing a gas to achieve the purpose of refining.
於現有的技術，作為黏結劑或增密劑的瀝青在製程中，往往因難以控制其縮聚的程度，造成縮聚過度而形成大面積的分子，使喹啉不溶物含量急遽上升及軟化點飆高，而過量的喹啉不溶物降低了瀝青的高溫流動性，並阻塞碳基材料氣孔，而影響增密劑的浸漬效果。且若瀝青的軟化點過高，在用作增密劑時，除增加操作成本外，過高的處理溫度亦可能讓瀝青再次縮聚成固態游離碳，而在高溫的情況下熱解形成氣體，而氣體則會殘留在瀝青內部造成缺陷。但若為了降低軟化點而降低中高分子物質的縮聚，由於瀝青內低分子量物質的比例相對較多，在高溫碳化等熱處理過程中，低分子量物質會大量的揮發，而降低了瀝青的結焦值。In the prior art, asphalt as a binder or densifier is often difficult to control the degree of polycondensation in the process, resulting in excessive polycondensation to form a large area of molecules, so that the quinoline insoluble content is rapidly increased and the softening point is high. Excess quinoline insolubles reduce the high temperature fluidity of the asphalt and block the pores of the carbon-based material, thereby affecting the impregnation effect of the densifier. And if the softening point of the asphalt is too high, in addition to increasing the operating cost when used as a densifying agent, an excessively high processing temperature may cause the asphalt to be polycondensed again into a solid free carbon, and at a high temperature, pyrolysis forms a gas. The gas will remain inside the asphalt causing defects. However, if the polycondensation of the medium-molecular substance is lowered in order to lower the softening point, since the proportion of the low-molecular-weight substance in the pitch is relatively large, in the heat treatment such as high-temperature carbonization, the low-molecular-weight substance is volatilized in a large amount, and the coking value of the pitch is lowered.
本發明之主要目的係提供一種用於提高碳基材料密度的增密劑，增密劑以精製瀝青的重量組份為100份，其特徵在於，增密劑包含： 重量組份為19~30的甲苯不溶物； 重量組份為0.1~0.3的喹啉不溶物； 重量組份為0~0.001的灰分；以及 重量組份為18~30的喹啉可溶物； 其中，精製瀝青的軟化點介於100℃~140℃之間。The main object of the present invention is to provide a densifying agent for increasing the density of a carbon-based material, the densifying agent having a weight component of the refined asphalt of 100 parts, wherein the densifying agent comprises: the weight component is 19-30 Toluene insolubles; quinoline insolubles having a weight component of 0.1 to 0.3; ash having a weight component of 0 to 0.001; and quinoline solubles having a weight component of 18 to 30; wherein the softening point of the refined asphalt Between 100 ° C ~ 140 ° C.
於上述較佳實施方式中，其中瀝青的結焦值範圍為56%~60%。In the above preferred embodiment, the coking value of the asphalt ranges from 56% to 60%.
於上述較佳實施方式中，其中精製瀝青的密度介於1.2g/cm3 ~1.3 g/cm3 之間。In the above preferred embodiment, the density of the refined asphalt is between 1.2 g/cm 3 and 1.3 g/cm 3 .
於上述較佳實施方式中，其中做為增密劑的精製瀝青的高溫碳產率範圍介於94%~96%。In the above preferred embodiment, the high-temperature carbon yield of the refined asphalt as the densifying agent ranges from 94% to 96%.
根據上述之目的，本發明所提供的精製瀝青由於其喹啉可溶物及甲苯不溶物含量較高，使其具有優良的黏結性能；而低含量的喹啉不溶物及低含量的灰分使精製瀝青具有良好的浸漬能力。According to the above object, the refined asphalt provided by the invention has excellent binding properties due to its high content of quinoline solubles and toluene insolubles, and low content of quinoline insolubles and low content of ash. Bitumen has good impregnation ability.
根據上述之目的，本發明所提供的精製瀝青由於軟化點較低，可避免瀝青再次縮聚成固態游離碳，使得在高溫下熱解成氣體的情況發生，並可降低操作成本；同時，較佳的結焦値也具體地反映在高密度碳基材料製作過程中的增密率與高溫碳產率，藉此，可減少對初階碳基材料熱勻壓增密的次數，有效地簡化製程及降低能量的耗損。According to the above object, the refined asphalt provided by the present invention can avoid the polycondensation of the asphalt into solid free carbon due to the lower softening point, so that pyrolysis into a gas at a high temperature occurs, and the operation cost can be reduced; The coking enthalpy is also specifically reflected in the densification rate and high-temperature carbon yield in the production process of high-density carbon-based materials, thereby reducing the number of times of initial homogenization of carbon-based materials, and effectively simplifying the process and Reduce energy consumption.
綜合上述之目的，使本發明所提供的精製瀝青進一步可作為一種增密劑或是具有黏結劑的增密劑的產品，而毋須再依黏結需求或增密需求調配不同的組份；故，本發明實為一極具產業價值之作。For the purpose of the above, the refined asphalt provided by the present invention can be further used as a densifier or a densifier having a binder, and it is not necessary to adjust different components according to the bonding demand or the densification requirement; The invention is actually a work of great industrial value.
本發明的優點及特徵以及達到其方法將參照例示性實施例及附圖進行更詳細的描述而更容易理解。然而，本發明可以不同形式來實現且不應被理解僅限於此處所陳述的實施例。相反地，對所屬技術領域具有通常知識者而言，所提供的此些實施例將使本揭露更加透徹與全面且完整地傳達本創作的範疇。The advantages and features of the present invention, as well as the methods thereof, will be more readily understood by reference to the exemplary embodiments and the accompanying drawings. However, the invention may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided to provide a thorough and complete and complete disclosure of the scope of the present invention.
本發明提供一種增密劑，主要成份為精製瀝青，在具有瀝青的增密劑可以提高石墨材料/碳基材料的密度。在本發明中，採用加壓通氣的方式，對重質油(中油, CPC004)進行熱反應處理，使得重質油中的輕分子量的物質不易散溢，而可保留於反應系統內，降低了反應物質的黏度，使得重分子量的物質可以容易地彼此聚合，此外，同時於熱反應系統中通入氧氣作為反應物質的交聯劑，藉此縮短熱反應的時間，並可以使反應溫度下降，透過反應溫度的下降使得反應物質的縮聚程度得以有效控制，而得到的產物即為增密劑，其中，反應條件:壓力範圍為0-10 大氣壓、反應時間0.5~2小時及氣體通入時間 0.5~2小時 以及反應溫度為380℃~430℃。藉由此種加壓與通入氧氣的反應條件，可提高瀝青的甲苯不溶物(QI)含量，且本實施例中，精製瀝青中的甲苯不溶物(QI)含量也比現有技術中的瀝青的甲苯不溶物(QI)含量高，因此可以製備獲得本發明的增密劑。其中增密劑，以精製瀝青的重量組份為100份，其包括：甲苯不溶物、喹啉不溶物、喹啉可溶物以及少量的灰分，其精製瀝青的物化性質如表1所示： 表1
由表1的量測結果顯示，由於反應時間的縮短以及反應溫度的下降，使得精製瀝青因縮聚而產生的喹啉不溶物(QI)的產量降低，由於本發明所提供的精製瀝青中所含有的喹啉不溶物的重量組份為0.1~0.3，使得最後形成的精製瀝青的軟化點溫度可維持在120℃~140℃之間。由於低含量的含喹啉不溶物，顯示出精製瀝青的純度高，無任何雜質，在增密過程無滲透阻力。且精製瀝青的結焦值為50%~60%，較佳的為56%~60%，顯示本發明精製瀝青中的重分子量的物質含量較多。本發明另一較佳的實施方式中，可將精製瀝青的軟化點溫度控制在100℃~140℃，較佳為120~140℃之間、且甲苯不溶物的重量組份大於30，使瀝青的結焦值大於53%，較佳值為大於56%。要說明的是，結焦值的計算方式是先將精製瀝青樣品稱重，其重量計為m，將坩堝烘乾後稱重，其重量計為m1，將精製瀝青樣品放置於坩堝內，並置於高溫爐中進行加熱，然後對坩堝連同坩堝內的殘渣一起稱重，其重量計為m2，利用結焦值計算公式 K=((m2-m1)/m)*100%，即可以得到精製瀝青的結焦值，上述公式中K值為煤瀝青結焦的數值，單位為(%)。另外，喹啉可溶物(QS)又稱β樹脂，其含量是甲苯不溶物(TI)的重量組份與喹啉不溶物(QI)的重量組份相減得到的數值，因此，精製瀝青內的β樹脂(即喹啉可溶物(QS)代表著精製瀝青本身黏結的能力，因此高品質的精製瀝青的β樹脂的含量是愈高愈好。The measurement results in Table 1 show that the yield of the quinoline insoluble matter (QI) produced by the polycondensation of the refined pitch is lowered due to the shortening of the reaction time and the decrease in the reaction temperature, and is contained in the refined asphalt provided by the present invention. The quinoline insoluble matter has a weight component of 0.1 to 0.3, so that the softening point temperature of the finally formed refined asphalt can be maintained between 120 ° C and 140 ° C. Due to the low content of quinoline-insoluble matter, it shows that the refined asphalt has high purity, no impurities, and no permeation resistance in the densification process. Moreover, the coking value of the refined asphalt is 50% to 60%, preferably 56% to 60%, which indicates that the content of the heavy molecular weight in the refined asphalt of the present invention is large. In another preferred embodiment of the present invention, the softening point temperature of the refined asphalt can be controlled between 100 ° C and 140 ° C, preferably between 120 and 140 ° C, and the weight component of the toluene insoluble matter is greater than 30, so that the asphalt The coking value is greater than 53%, and preferably greater than 56%. It should be noted that the coking value is calculated by weighing the refined asphalt sample first, and the weight is m. The 坩埚 is dried and weighed, and the weight is m1. The refined asphalt sample is placed in the crucible and placed. Heating in a high-temperature furnace, and then weighing the crucible together with the residue in the crucible, the weight is m2, and using the coking value calculation formula K=((m2-m1)/m)*100%, the refined asphalt can be obtained. The coking value, the value of K in the above formula is the value of coal tar coking, and the unit is (%). Further, the quinoline soluble substance (QS) is also called a β resin, and the content thereof is a value obtained by subtracting the weight component of the toluene-insoluble matter (TI) from the weight component of the quinoline insoluble matter (QI), and therefore, the refined asphalt The β-resin (i.e., quinoline solubles (QS)) represents the ability of the refined asphalt itself to bond, so the higher the content of the β-resin of the high-quality refined asphalt, the better.
以精製瀝青作為黏結劑製備初階碳基材料:Preparation of preliminary carbon-based materials using refined asphalt as a binder:
實施例1Example 1
請參閱圖2，圖2為以精製瀝青作為具有黏結劑的增密劑製備初階碳基材料的示意圖，將石墨粉1與含精製瀝青的具有黏結劑2的增密劑混和，經過擠壓成型後，即可獲得初階碳基材料3。在本實施例中，喹啉可溶物為增密劑中提供具有黏結作用的主要成分，因此本發明所提供的精製瀝青具有可作為製備初階碳基材料的黏結功能。Please refer to FIG. 2 , which is a schematic diagram of preparing a preliminary carbon-based material by using refined asphalt as a densifier having a binder, and mixing graphite powder 1 with a densifier having a binder 2 and containing a refined asphalt, and extruding. After the molding, the preliminary carbon-based material 3 can be obtained. In the present embodiment, the quinoline soluble material provides a main component having a bonding function in the densifying agent, and therefore the refined asphalt provided by the present invention has a bonding function as a preliminary carbon-based material.
以精製瀝青作為增密劑以製備高密度碳基材料Using refined asphalt as a densifier to prepare high density carbon-based materials
實施例2Example 2
請繼續參閱圖3，圖3為以精製瀝青作為增密劑以製備高密度碳基材料的示意圖，首先將初階碳基材料3放置於容器4中，並加入含精製瀝青的增密劑5進行浸潤，爾後，以溫度600℃以上、壓力為12000PSI(pounds per square inch)的條件下，對初階碳基材料3進行熱勻壓增密(HIP)，接著以溫度900℃以上、反應時間2小時的條件下進行碳化反應，最後再以溫度2300℃以上、反應時間1小時的條件下進行石墨化反應，即可獲得高密度碳基材料6，若為提高高密度碳基材料6的密度，則可讓高密度碳基材料6重複二次、三次或多次熱勻壓增密的步驟。其中，初階碳基材料3可以圖2的方式製備，亦可直接購買市售的石墨塊材(密度約為1.7g/cm3 ~1.8g/cm3 )。Please refer to FIG. 3 again. FIG. 3 is a schematic diagram of preparing a high-density carbon-based material by using refined asphalt as a densifying agent. First, the preliminary carbon-based material 3 is placed in the container 4, and a densifier containing refined asphalt is added. After the wetting, the preliminary carbon-based material 3 is subjected to heat homogenization (HIP) at a temperature of 600 ° C or higher and a pressure of 12,000 PSI (pounds per square inch), followed by a temperature of 900 ° C or higher and a reaction time. The carbonization reaction is carried out under the conditions of 2 hours, and finally the graphitization reaction is carried out under the conditions of a temperature of 2300 ° C or more and a reaction time of 1 hour to obtain a high-density carbon-based material 6 if the density of the high-density carbon-based material 6 is increased. Then, the high-density carbon-based material 6 can be repeated for the second, third or more heat homogenization and densification steps. Among them, the preliminary carbon-based material 3 can be prepared in the manner of FIG. 2, or a commercially available graphite block (having a density of about 1.7 g/cm 3 to 1.8 g/cm 3 ) can be directly purchased.
為測試本發明增密劑的效果，分別對美國指標產品A240、含本發明精製瀝青的增密劑EX1、EX2及EX3進行物化性質及增密表現測試，其中，物化性質測試包括：軟化點(℃)、甲苯不溶物、喹啉不溶物、灰分及固定碳/結焦値(%)，測試結果如表2所示；增密表現測試則進一步測試高密度碳基材料的特性，包括：初階碳基材料原始密度(g/cm3
)、一次增密碳基材料密度(g/cm3
)、一次增密率(%)、熱膨脹係數(*10-6
/K)及高溫碳產率(%)，測試結果如表3所示： 表2
由表2及表3的結果得知，由於本發明所提供的精製瀝青其內含的喹啉不溶物之重量組份小於0.3，較佳範圍的重量組份為0.1~0.3，且其灰分的含量較市售美國指標產品 A240為低，甚至於不含灰分的存在，顯示含有精製瀝青的增密劑在增密過程中灰份愈少，愈有利於精製瀝青的浸漬能力。而中溫的軟化點，可避免過高的處理溫度讓精製瀝青再次縮聚成固態游離碳，而在高溫的情況下熱解形成氣體。From the results of Table 2 and Table 3, since the refined asphalt provided by the present invention has a quinoline insoluble content of less than 0.3, the preferred range of the weight component is 0.1 to 0.3, and the ash content thereof is The content is lower than that of the commercially available American index product A240, even in the absence of ash, indicating that the densifier containing refined asphalt has less ash in the densification process, and the more favorable the impregnation ability of the refined asphalt. The softening point of the medium temperature can avoid excessive treatment temperature, so that the refined asphalt is again polycondensed into solid free carbon, and pyrolysis forms a gas at high temperature.
此外，由於高分子量較多，其固定碳/結焦値優於市售美國指標產品 A240，且高固定碳/結焦値的特性亦讓高密度碳基材料的一次增密率接近或大於5%，以及高溫碳產率範圍介於92%~96%，較佳值為94%~96%，其效果整體效果優於市售美國指標產品 A240(如表3所示)。所製備出的高密度碳基材料其熱膨脹係數亦小於5%，不因密度的增加而升高，使製作出的高密度碳基材料更加符合後續製程的需求。在此要說明的是，由於精製瀝青的浸漬過程都在高溫高壓的環境下進行，因此，高溫碳產率格外重要。在本發明中，高溫碳產率定義是指，在經過高溫反應一段時間後，碳所殘留下來的百分率。由於高溫碳產率是與碳材料的浸漬有關，所以在本發明的實施例中證明了在經過高溫浸漬之後，能留下來的碳愈多則表示高溫碳產率愈好。In addition, due to the high molecular weight, its fixed carbon/coking enthalpy is superior to the commercially available American index product A240, and the high fixed carbon/coking enthalpy characteristics also make the high density carbon-based material have a densification rate close to or greater than 5%. And the high temperature carbon yield range is 92%~96%, preferably 94%~96%, and the overall effect is better than the commercially available American index product A240 (as shown in Table 3). The prepared high-density carbon-based material has a coefficient of thermal expansion of less than 5%, and does not increase due to an increase in density, so that the produced high-density carbon-based material is more in line with the requirements of subsequent processes. It should be noted here that since the impregnation process of the refined asphalt is carried out in a high temperature and high pressure environment, the high temperature carbon yield is particularly important. In the present invention, the definition of high temperature carbon yield refers to the percentage of carbon remaining after a period of high temperature reaction. Since the high-temperature carbon yield is related to the impregnation of the carbon material, it has been demonstrated in the examples of the present invention that the more carbon remaining after the high-temperature impregnation, the better the high-temperature carbon yield.
高溫燒蝕率測試High temperature ablation rate test
實施例3Example 3
請繼續參閱圖4，圖4為發動機燒蝕靜試驗證流程示意圖，於圖4中，先將圖3中的高密度碳基材料6加工製成石墨噴喉7，其中，A代表石墨噴喉7的正視圖；B代表石墨噴喉7的側視剖面圖，正視圖A顯示石墨噴喉7具有喉徑71。隨後，以發出溫度2000℃以上火焰的發動機對石墨噴喉7進行燒蝕靜試，圖4中，發動機所發出火焰8會通過石墨噴喉7，測試時間會持續3~4秒，此時會測試通過石墨噴喉7的平均壓力(kgf/cm2
)及平均推力(kgf)，待測試結束後，進一步量測喉徑71的變化，得到喉徑71的燒蝕量與單次燒蝕率。其中，分別以美國指標產品 A240與本發明所提供含精製
瀝青的增密劑EX 1、EX2製備的高密度碳基材料6所製成的石墨噴喉7進行高溫燒蝕率測試，測試結果如表4所示： 表4
由表4的結果得知，以美國指標產品 A240製成的石墨噴喉7，其平均燒蝕率為0.097mm/s，以本發明增密劑EX1、EX2製成的石墨噴喉7，其平均燒蝕率分別為0.085mm/s及0.116mm/s，顯示以本發明增密劑EX1、EX2製成的石墨噴喉7其口徑變化程度不大，其燒蝕量仍維持在一定的水準，且相較美國指標產品 A240製成的石墨噴喉7，增密劑EX1製成的石墨噴喉7具有更突出的耐燒蝕能力。由此得知，以含本發明瀝青的增密劑具有優良的黏結性能。From the results of Table 4, it is known that the graphite ablation throat 7 made of the American index product A240 has an average ablation rate of 0.097 mm/s, and the graphite throat throat 7 made of the densifiers EX1 and EX2 of the present invention has an average value. The ablation rates are 0.085 mm/s and 0.116 mm/s, respectively, indicating that the graphite spray nozzle 7 made of the densifiers EX1 and EX2 of the present invention has a small degree of change in caliber, and the ablation amount is maintained at a certain level, and Compared with the graphite spray throat 7 made by the American index product A240, the graphite spray throat 7 made of the densifier EX1 has more outstanding ablation resistance. From this, it is known that the densifying agent containing the pitch of the present invention has excellent bonding properties.
綜上所述，本發明所提供的精製瀝青由於其甲苯不溶物含量較高，使其具有優良的黏結性能，而低含量的喹啉不溶物及低含量或無灰分使精製瀝青具有良好的浸漬能力。另一方面，由於軟化點較低，可避免瀝青再次縮聚成固態游離碳而在高溫下熱解成氣體的情況發生。此外，較佳的結焦値也具體地反映在高密度碳基材料製作過程中的增密率與高溫碳產率，藉此，可減少對初階碳基材料熱勻壓增密的次數，有效地簡化製程及降低能量的耗損。基於上述特性，使本發明所提供的精製瀝青可作為增密劑或是具有黏結劑的增密劑，而毋須再依黏結需求或增密需求調配不同的組份；故，本發明實為一極具產業價值之作。In summary, the refined asphalt provided by the present invention has excellent cohesive properties due to its high content of toluene insoluble matter, and low content of quinoline insoluble matter and low content or no ash makes the refined asphalt have good impregnation. ability. On the other hand, since the softening point is low, it can be avoided that the pitch is again polycondensed into solid free carbon and pyrolyzed into a gas at a high temperature. In addition, the preferred coking enthalpy is also specifically reflected in the densification rate and high-temperature carbon yield in the production process of the high-density carbon-based material, thereby reducing the number of times of heat-densification and densification of the preliminary carbon-based material, and effectively Simplify the process and reduce energy consumption. Based on the above characteristics, the refined asphalt provided by the present invention can be used as a densifying agent or a densifying agent having a binder, and it is not necessary to mix different components according to the bonding requirement or the densification requirement; therefore, the present invention is one. Very industrial value.
本發明得由熟悉本技藝之人士任施匠思而為諸般修飾，然皆不脫如附申請專利範圍所欲保護。The present invention is intended to be modified by those skilled in the art, and is not intended to be limited by the scope of the appended claims.
1‧‧‧石墨粉1‧‧‧Graphite powder
2‧‧‧含精製瀝青的具有黏結劑的增密劑2‧‧‧Densifier with binder for refined asphalt
3‧‧‧初階碳基材料3‧‧‧First-order carbon-based materials
4‧‧‧容器4‧‧‧ Container
5‧‧‧含精製瀝青的增密劑5‧‧‧Densifier containing refined asphalt
6‧‧‧高密度碳基材料6‧‧‧High-density carbon-based materials
7‧‧‧石墨噴喉7‧‧‧Maple Throat
8‧‧‧火焰8‧‧‧flame
A‧‧‧正視圖A‧‧‧ front view
B‧‧‧側視剖面圖B‧‧‧Side view
C1‧‧‧瀝青C1‧‧‧Asphalt
C11‧‧‧甲苯不溶物(TI)C11‧‧‧Toluene insolubles (TI)
C12‧‧‧甲苯可溶物(TS)(γ樹脂)C12‧‧‧Toluene solubles (TS) (γ resin)
C111‧‧‧喹啉不溶物(QI)(α樹脂)C111‧‧‧Quinoline insolubles (QI) (alpha resin)
C112‧‧‧喹啉可溶物(QS) (β樹脂)C112‧‧‧Quinoline solubles (QS) (β resin)
圖1為瀝青組份示意圖； 圖2為以精製瀝青作為具有黏結劑的增密劑以製備初階碳基材料的示意圖； 圖3為以精製瀝青作為增密劑以製備高密度碳基材料的示意圖；及 圖4係為發動機燒蝕靜試驗證流程示意圖。1 is a schematic view of an asphalt component; FIG. 2 is a schematic view of a refined asphalt as a densifier having a binder to prepare a preliminary carbon-based material; and FIG. 3 is a schematic diagram of using a refined asphalt as a densifier to prepare a high-density carbon-based material. Schematic diagram; and Figure 4 is a schematic diagram of the engine ablation test.
Claims (5)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259171A (en) * | 1978-03-10 | 1981-03-31 | Rutgerswerke Aktiengesellschaft | Process for the separation of quinoline-insoluble components from coal tar pitch |
| US4806228A (en) * | 1986-02-07 | 1989-02-21 | Rutgerswerke Ag | Process for producing pitch raw materials |
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- 2017-01-20 TW TW106139086A patent/TWI642729B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259171A (en) * | 1978-03-10 | 1981-03-31 | Rutgerswerke Aktiengesellschaft | Process for the separation of quinoline-insoluble components from coal tar pitch |
| US4806228A (en) * | 1986-02-07 | 1989-02-21 | Rutgerswerke Ag | Process for producing pitch raw materials |
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