TW202335833A - Method for forming layered thermoset silicone and thermoplastic articles using additive manufacturing, articles formed therefrom and apparatus for use therein - Google Patents
Method for forming layered thermoset silicone and thermoplastic articles using additive manufacturing, articles formed therefrom and apparatus for use therein Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/205—Means for applying layers
- B29C64/209—Heads; Nozzles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Abstract
Description
本發明係關於增材製造，特定言之包含熱固性彈性體之複合物，包括具有含聚矽氧烷彈性體之複合物經由熔融長絲製造及沈積進行之增材製造的領域。The present invention relates to the field of additive manufacturing, particularly of composites containing thermoset elastomers, including the additive manufacturing of composites containing polysiloxane elastomers via molten filament fabrication and deposition.
增材製造通常亦被稱為三維（「3D」）列印，對於物件之快速原型設計及商業製造愈來愈普及。已知各種類型之增材製造製程，包括：槽光聚合方法，諸如立體微影（「stereolithography；SLA」）；材料或黏合劑噴射方法；粉末床熔融方法，諸如選擇性雷射燒結（「selective laser sintering；SLS」）；及材料擠壓方法，諸如熔融沈積成型（「fused deposition modeling；FDM」）、熔融長絲製造（「fused-filament fabrication；FFF」）及直接丸粒擠壓以及其他方法。Additive manufacturing, also commonly referred to as three-dimensional (“3D”) printing, is becoming increasingly popular for rapid prototyping and commercial manufacturing of objects. Various types of additive manufacturing processes are known, including: slot polymerization methods such as "stereolithography (SLA)"; material or binder jetting methods; powder bed fusion methods such as "selective laser sintering" ("selective laser sintering"). laser sintering (SLS)); and material extrusion methods such as fused deposition modeling (FDM), fused-filament fabrication (FFF), and direct shot extrusion, among other methods .
在槽光聚合方法中，液體光聚合物樹脂儲存於安置建構平台之槽中。可基於物件之電腦模型形成物件，在該電腦模型中該物件表示為一系列層或橫截面。基於電腦模型，使用UV光選擇性固化液體光聚合物樹脂來形成物件之第一層。一旦形成第一層，則降低建構平台，且使用UV光固化液體光聚合物樹脂，以便在第一層頂部上形成物件之後續層。重複此製程，直至形成列印物件為止。In the tank photopolymerization method, liquid photopolymer resin is stored in a tank that houses the build platform. The object may be formed based on a computer model of the object in which the object is represented as a series of layers or cross-sections. Based on computer models, UV light is used to selectively cure liquid photopolymer resin to form the first layer of the object. Once the first layer is formed, the build platform is lowered and a UV light is used to cure the liquid photopolymer resin to form subsequent layers of the object on top of the first layer. Repeat this process until the printed object is formed.
在材料噴射方法中，藉由沈積液體材料，諸如熱固性光聚合物之液滴，從而基於物件之電腦模型形成物件之第一層，以逐層方式製備物件。液體材料之沈積層諸如藉由施加UV光來固化或凝固。後續層以相同方式沈積，以便製造列印物件。在黏合劑噴射中，藉由將一層粉末狀材料沈積在建構平台上且選擇性沈積液體黏合劑以接合粉末來形成物件。粉末及黏合劑之後續層以相同方式沈積，且黏合劑充當粉末層之間的黏著劑。In material jetting methods, objects are prepared in a layer-by-layer manner by depositing droplets of liquid material, such as thermosetting photopolymers, to form the first layer of the object based on a computer model of the object. The deposited layer of liquid material is cured or solidified, such as by application of UV light. Subsequent layers are deposited in the same manner to create the printed object. In adhesive jetting, an object is formed by depositing a layer of powdered material onto a building platform and selectively depositing a liquid adhesive to join the powder. Subsequent layers of powder and binder are deposited in the same manner, with the binder acting as a cohesive agent between the powder layers.
在粉末床熔融方法，且具體言之SLS中，物件藉由生成待列印之物件的電腦模型形成，其中物件表示為一系列層或橫截面。為了製備該物件，將一層粉末沈積在建構平台上，且粉末藉由使用雷射燒結以基於電腦模型形成一層物件。一旦該層經燒結，則將另一層粉末沈積且燒結。視需要重複此製程，以形成具有所要組態之物件。In powder bed fusion methods, and specifically SLS, objects are formed by generating a computer model of the object to be printed, where the object is represented as a series of layers or cross-sections. To prepare the object, a layer of powder is deposited on a building platform, and the powder is sintered using a laser to form a layer of the object based on the computer model. Once this layer is sintered, another layer of powder is deposited and sintered. Repeat this process as necessary to form the object with the desired configuration.
在材料擠壓方法，諸如FDM或FFF中，生成物件之電腦模型，其中物件表示為一系列層。物件藉由將材料之長絲饋入擠壓頭中來製造，該擠壓頭加熱長絲，且將經加熱長絲沈積在基板上以形成一層物件。一旦層形成，則擠壓頭繼續根據物件之電腦模型沈積物件之下一層。以逐層方式重複此製程，直至完全形成列印物件為止。類似地，在直接丸粒擠壓中，將丸粒而非長絲用作饋入材料，且將丸粒饋入擠壓頭中，且加熱及沈積至基板上。In material extrusion methods, such as FDM or FFF, a computer model of an object is generated, in which the object is represented as a series of layers. Objects are made by feeding filaments of material into an extrusion head, which heats the filaments and deposits the heated filaments onto a substrate to form a layer of the object. Once the layer is formed, the extrusion head continues to deposit the layer below the part based on a computer model of the part. Repeat this process layer by layer until the printed object is completely formed. Similarly, in direct pellet extrusion, pellets rather than filaments are used as the feed material, and the pellets are fed into the extrusion head, heated and deposited onto the substrate.
已知多種聚合材料用於增材製造方法中。用於增材製造之常見聚合材料包括丙烯腈丁二烯苯乙烯（acrylonitrile butadiene styrene；ABS）、聚胺甲酸酯、聚醯胺、聚苯乙烯及聚乳酸（polylactic acid；PLA）。最近，高效能工程熱塑性塑膠已用於製造相對於常見聚合物材料具有改良之機械及化學特性的列印物件。該等高效能熱塑性塑膠包括聚芳基醚酮、聚苯基碸、聚碳酸酯及聚醚醯亞胺。A variety of polymeric materials are known for use in additive manufacturing methods. Common polymer materials used in additive manufacturing include acrylonitrile butadiene styrene (ABS), polyurethane, polyamide, polystyrene, and polylactic acid (PLA). Recently, high-performance engineering thermoplastics have been used to create printed objects with improved mechanical and chemical properties relative to common polymer materials. Such high-performance thermoplastics include polyaryl ether ketone, polyphenylene sulfide, polycarbonate and polyetherimide.
儘管增材製造方法可用於快速形成具有不同形狀及組態中之任一者的物件，但藉由增材製造製程形成之物件可能存在在列印物件之z方向上層間黏附弱的問題。Although additive manufacturing methods can be used to quickly form objects with any of different shapes and configurations, objects formed by the additive manufacturing process may suffer from weak interlayer adhesion in the z-direction of the printed object.
當前，基於FFF及FDM使用材料擠壓三維列印（material extrusion three-dimensional printing；ME3DP）進行之增材製造被視為係高度靈活且有效的增材製造技術。在此製程中，將熱塑性長絲加熱，且隨後「擠壓」，且熔融至底層上。在彼技術領域中此技術被視為可能適用於使用電腦輔助設計開發具有更複雜幾何結構之製造組件。Currently, additive manufacturing based on FFF and FDM using material extrusion three-dimensional printing (ME3DP) is regarded as a highly flexible and effective additive manufacturing technology. In this process, thermoplastic filaments are heated and then "extruded" and fused to a base layer. This technology is viewed as potentially suitable for use in the field of technology to develop manufacturing components with more complex geometries using computer-aided design.
除使用如上文提及之所用材料之外，已進一步嘗試開發使用FFF列印柔軟熱塑性彈性體，諸如乙烯乙酸乙烯酯（ethylene vinyl acetate；EVA）、含乙烯-丙烯二烯單體之聚丙烯基質（ethylene-propylene diene monomer in a polypropylene matrix；EPDM + PP）、丙烯腈-丁二烯-苯乙烯（ABS）及苯乙烯-乙烯-丁二烯-苯乙烯（styrene-ethylene-butadiene-styrene；SEBS）的技術。然而，該等材料在使用FFF處理以形成物件方面存在挑戰。參見N Kumar等人, 「3D Printing of Flexible Parts Using EVA Material」, Materials Physics and Mechanics 37, 第124-132頁(2018)；N. Kumar等人, 「Additive Manufacturing of Flexible Electrically Conductive Polymer Compositions Using CNC-Assisted Fused Layer Modeling Process」, Journal of the Brazilian Society of Mechanical Sciences and Engineering, 40:175 (2018)及K. Elkins等人, 「Soft Elastomers for Fused Deposition Modeling」, Virginia Polytechnic Institute and State University, the International Solid Freeform Fabrication Symposium (1997)中呈現。In addition to using materials such as those mentioned above, further attempts have been made to develop FFF printing soft thermoplastic elastomers, such as ethylene vinyl acetate (EVA), polypropylene matrices containing ethylene-propylene diene monomers (ethylene-propylene diene monomer in a polypropylene matrix; EPDM + PP), acrylonitrile-butadiene-styrene (ABS) and styrene-ethylene-butadiene-styrene (SEBS) ) technology. However, these materials present challenges in using FFF processing to form objects. See N. Kumar et al., “3D Printing of Flexible Parts Using EVA Material,” Materials Physics and Mechanics 37, pp. 124-132 (2018); N. Kumar et al., “Additive Manufacturing of Flexible Electrically Conductive Polymer Compositions Using CNC- Assisted Fused Layer Modeling Process", Journal of the Brazilian Society of Mechanical Sciences and Engineering, 40:175 (2018) and K. Elkins et al., "Soft Elastomers for Fused Deposition Modeling", Virginia Polytechnic Institute and State University, the International Solid Presented in Freeform Fabrication Symposium (1997).
由於該等材料係柔軟的，因此其對於許多應用往往缺乏足夠的壓縮形變及耐熱性。為了提供更佳的效能，該等材料一般經製備以混配彈性體（亦即用於硫化之可固化彈性體組成物，包括可固化聚合物、一或多種填料，且一般亦包括固化系統）之形式使用。在該等材料經處理時，其在交聯橡膠系統中形成網狀結構，此可能不利地影響使用分層FFF技術製造物體之能力。此項技術中需要開發此類技術，因為該等網狀結構提供成品應包括強界面黏合的可能性，其限制條件為存在用FFF或另一種增材技術成功形成該等網狀結構的能力。Because these materials are soft, they often lack sufficient compression set and heat resistance for many applications. In order to provide better performance, these materials are generally prepared to compound elastomers (i.e., a curable elastomeric composition for vulcanization, including a curable polymer, one or more fillers, and generally a curing system) form used. When these materials are processed, they form a network structure in the cross-linked rubber system, which may adversely affect the ability to manufacture objects using layered FFF technology. There is a need to develop such techniques in this technology because these mesh structures offer the possibility that the finished product should include strong interfacial bonding, subject to the existence of the ability to successfully form these mesh structures with FFF or another additive technology.
對於在彈性體領域中開發可增材處理化合物，此項技術中進一步存在以下問題：充分混配之可固化彈性組成物之處理特徵與熱塑性塑膠，諸如典型地用於FFF處理的上文提及之熱塑性塑膠之處理特徵十分不同。當嘗試將彈性體以可固化混配形式引入增材製造製程中，特定言之在熱固性彈性體之情況下時，出於能夠在固化材料之前處理其之目的，必須注意使材料保持低於其固化溫度。該等材料在未充分加熱時存在針對處理的其他挑戰，因為其一般具有高黏度（通常由施加熱量解決之問題）。因此，難以維持可處理性，同時亦嘗試防止或阻止在處理期間且在有意固化之前交聯形成。For the development of additively processable compounds in the field of elastomers, there are further problems in this technology: the processing characteristics of well-combined curable elastomeric compositions with thermoplastics, such as those mentioned above that are typically used for FFF processing. The processing characteristics of thermoplastics are very different. When attempting to introduce elastomers into additive manufacturing processes in curable compound form, specifically in the case of thermoset elastomers, care must be taken to keep the material below its Curing temperature. These materials present additional challenges for processing when insufficiently heated, as they typically have high viscosity (a problem typically solved by applying heat). Therefore, it is difficult to maintain processability while also trying to prevent or prevent crosslink formation during processing and prior to intentional curing.
由於存在該等黏度材料及固化防止需要，包括需要防止由於在加熱以供處理時長絲彎曲而出現的問題，使用當前可用三維列印設備饋入可撓性長絲亦造成另一挑戰。Feeding flexible filaments using currently available 3D printing equipment also poses another challenge due to the presence of these viscous materials and the need to prevent solidification, including the need to prevent problems due to bending of the filaments when heated for processing.
在列印聚矽氧烷及其複合物時出現該等問題。該等材料有可能在諸如醫療航太、消費型產品及製造業等廣泛領域中實現許多需要低模數彈性材料之終端應用，諸如醫療裝置、密封墊及O型環組件、可撓性柔軟電子件及食品包裝的可調功能性及異質結構特性。模製該等材料係可行的，但對於大部件製造而言成本高，且無法再利用之模具及模成本高。設計的改變需要進一步開發新工具。因此，此項技術中需要利用增材製造形成該等部件同時亦提供強化體以使增材製造更可行的能力。The problem occurs when printing polysiloxane and its composites. These materials have the potential to enable many end applications requiring low modulus elastomeric materials, such as medical devices, gasket and O-ring components, flexible and flexible electronics, in a wide range of fields such as medical aerospace, consumer products and manufacturing. Adjustable functionality and heterogeneous structural properties of parts and food packaging. Molding these materials is possible, but is costly for large parts, and the cost of molds and molds that cannot be reused is high. Changes in design require further development of new tools. Therefore, what is needed in this technology is the ability to use additive manufacturing to form these parts while also providing reinforcements to make additive manufacturing more feasible.
在增材製造領域中，直接墨水書寫（direct ink writing；DIW）已用於中尺度及微尺度結構以產生複雜柔軟組件。在DIW中逐層製造三維結構包括經由具有指定壓力之噴嘴擠壓液相墨水且用數位界定之路徑進行沈積。與FDM相比，DIW典型地將需要經歷列印後固化或燒結以固結列印結構且達成機械強度。各種類型之DIW（例如，基於小液滴或基於連續糊狀物）係可用的且DIW可用於許多類型之材料。當製備列印墨水時，流變及機械特性為關鍵考慮因素，前者控制墨水之調配製程以評估可列印性，且後者特性，諸如剛性及強度必須經選擇以產生穩定且功能性結構而不坍落變形或崩塌。在聚矽氧烷之增材列印中，使用立體微影及數位光處理為使用單一聚矽氧烷墨水界定三維聚矽氧烷結構之常用方法。然而，該等技術對於少量列印而言相對昂貴。DIW材料擠壓為目前列印聚矽氧烷之熟知方式，因為噴嘴分配方法可滿足自低黏度液體至糊狀物之廣泛範圍之流體的沈積要求。氣動、壓力致動及機械系統可用於分配用於材料擠壓之流體。In the field of additive manufacturing, direct ink writing (DIW) has been used in mesoscale and microscale structures to produce complex soft components. Layer-by-layer fabrication of three-dimensional structures in DIW involves squeezing liquid ink through a nozzle with a specified pressure and depositing it in a digitally defined path. Compared to FDM, DIW will typically need to undergo post-printing curing or sintering to consolidate the printed structure and achieve mechanical strength. Various types of DIW are available (eg, based on small droplets or based on continuous paste) and DIW can be used with many types of materials. When preparing printing inks, rheological and mechanical properties are key considerations. The former controls the ink formulation process to assess printability, and the latter properties, such as stiffness and strength, must be selected to produce stable and functional structures without Slump deformation or collapse. In additive printing of polysiloxane, the use of stereolithography and digital light processing are common methods for defining three-dimensional polysiloxane structures using a single polysiloxane ink. However, these technologies are relatively expensive for low-volume printing. DIW material extrusion is currently a well-known method for printing polysiloxane because the nozzle distribution method can meet the deposition requirements of a wide range of fluids from low-viscosity liquids to pastes. Pneumatic, pressure-actuated, and mechanical systems can be used to distribute fluid for material extrusion.
然而，該等材料之弱點持續存在，且此項技術中需要發現充分強化其之方式。短纖及短強化纖維或添加劑可用於誘導電學特性或改良機械強度。亦已嘗試其他技術，諸如改變纖維位向及微調流變或機械特性，包括併入天然纖維以降低碳或玻璃之短纖維的成本，然而，此項技術中之需要繼續存在。為了真正地增加強度，需要長纖維強化體或其他技術。為此之嘗試包括預浸漬長絲以及共擠壓，纖維囊封及其類似方法亦已嘗試，但高成本、低黏附及缺少外部保護使該等方法尚不適合於較大規模製造。However, weaknesses in these materials persist, and ways to adequately strengthen them need to be discovered in this technology. Short fibers and short reinforcing fibers or additives can be used to induce electrical properties or improve mechanical strength. Other techniques have also been attempted, such as changing fiber orientation and fine-tuning rheological or mechanical properties, including incorporation of natural fibers to reduce the cost of short fibers of carbon or glass, however, the need for this technology continues to exist. To really add strength, long fiber reinforcements or other techniques are needed. Attempts to this end include pre-impregnated filaments and co-extrusion. Fiber encapsulation and similar methods have also been tried, but high cost, low adhesion and lack of external protection make these methods not yet suitable for larger-scale manufacturing.
已開發出連續纖維強化複合物用於增材製造製程以製備重量輕且機械特性高的各種複雜結構。然而，迄今為止，增材列印材料由於基於擠壓之列印製程而具有機械異向性，該製程在沈積製程期間產生小的幾何形狀變化，其影響最終部件之方向強度。因此，需要強化該等材料。Continuous fiber-reinforced composites have been developed for use in additive manufacturing processes to prepare various complex structures with light weight and high mechanical properties. However, to date, additive printing materials have mechanical anisotropy due to the extrusion-based printing process, which produces small geometric changes during the deposition process that affect the directional strength of the final part. Therefore, there is a need to strengthen such materials.
亦已嘗試藉由使用擠壓頭來解決結構支撐之問題，該擠壓頭經組態以在單一共擠壓三維列印設備頭中將某些熱塑性塑膠（諸如耐綸）或某些可固化熱固物（諸如基於環氧樹脂或胺基甲酸酯之彈性體）擠壓至纖維強化體上方，其中在一些情況下，纖維可為單一纖維或預浸漬束。以此方式製得之經碳纖維、Kevlar®或Fiberglass®列印材料強化之耐綸可獲自Markforged公司。使用某些彈性體（包括聚矽氧烷）之共擠壓纖維（諸如碳纖維）可獲自Continuous Composites公司。該等材料及製程亦描述於例如美國專利第10,449,711號及第10,603,836號、美國專利公開案第2020/00369360 A1號及國際專利申請公開案第WO 2021/173795 A2號中。在一些情況下，Attempts have also been made to solve the problem of structural support by using extrusion heads configured to combine certain thermoplastics (such as nylon) or certain curable A thermoset, such as an epoxy or urethane-based elastomer, is extruded over the fiber reinforcement, where in some cases the fibers may be single fibers or pre-impregnated bundles. Nylon produced in this manner and reinforced with carbon fiber, Kevlar® or Fiberglass® printing materials is available from Markforged. Coextruded fibers (such as carbon fibers) using certain elastomers, including polysiloxanes, are available from Continuous Composites. These materials and processes are also described in, for example, U.S. Patent Nos. 10,449,711 and 10,603,836, U.S. Patent Publication No. 2020/00369360 A1, and International Patent Application Publication No. WO 2021/173795 A2. In some cases,
儘管迄今為止已出現發展，但仍需要尋找一種將允許列印高效能彈性體，諸如由亦適合於最終用途之可固化熱固性含矽聚合物形成的聚矽氧烷彈性體之方法，該等最終用途諸如但不限於半導體、井下工具、醫療裝置、航空太空、防禦及不同其他應用及市場中之用途，然而，許多該等部分除了必須用於廣泛範圍之操作環境中之外，亦需要形成複雜幾何結構，且需要經濟的形成製程，該等製程在列印時具有更強的層間黏附以滿足最終用途的需求。Despite the developments to date, there remains a need to find a method that will allow for the printing of high performance elastomers, such as polysiloxane elastomers formed from curable thermoset silicon-containing polymers that are also suitable for end-use applications. Uses such as, but not limited to, use in semiconductors, downhole tools, medical devices, aerospace, defense, and various other applications and markets, however, many of these parts, in addition to having to be used in a wide range of operating environments, also require complex geometries and require economical formation processes that have stronger interlayer adhesion when printing to meet end-use requirements.
本發明呈現解決先前技術中之上述問題的方式。本文中申請人介紹的降低形成該等部分之成本及/或改變其特性以達成可接受最終用途特性的一種方式將為調適增材製造方法，該方法使得能夠藉由引入具有該等彈性體之另一種材料來引入難以列印及/或列印昂貴的彈性體之複合物。形成經由增材製造製備的此類複合物在複合物中提供一種材料以強化及幫助增強該彈性體，同時亦降低製造成本，且使得使用該等彈性體進行物件的製備更易於三維列印。本文中申請人介紹的另一方式為介紹製備藉由增材製造形成之長纖維強化高效能彈性體材料的方式。因此，雖然此項技術中需要增材製造包括高效能彈性體之複合物部分，其可提供多種通用特性，同時維持低成本製造方法，但該等需要由本文中之申請人的方法、複合物及列印物件實現。The present invention presents a way to solve the above-mentioned problems in the prior art. Applicants describe herein that one way to reduce the cost of forming such parts and/or modify their properties to achieve acceptable end-use properties would be to adapt additive manufacturing methods that enable the production of components by incorporating elastomers with such elastomers. Another material to incorporate elastomers into the composite that are difficult to print and/or expensive to print. Forming such composites produced through additive manufacturing provides a material in the composite to strengthen and help strengthen the elastomer, while also reducing manufacturing costs and making it easier to three-dimensionally print objects made using these elastomers. Another method introduced by the applicant in this article is to introduce a method of preparing long fiber reinforced high-performance elastomeric materials formed by additive manufacturing. Therefore, while there is a need in the art to additively manufacture composite portions including high-performance elastomers that can provide a variety of versatile properties while maintaining low-cost manufacturing methods, such needs are determined by Applicant's methods herein, composite and print object implementation.
本發明包括一種形成包含熱固性含矽聚合物之複合物件的方法及其方法所形成的物件以及與其方法相關的設備。本揭示案包括以下具體實例中之一或多者。The present invention includes a method of forming a composite article comprising a thermosetting silicon-containing polymer, the articles formed by the method, and equipment associated with the method. The present disclosure includes one or more of the following specific examples.
在一個具體實例中，本發明包括一種形成包含熱固性含矽聚合物之複合物件之方法，該方法包含：提供包含第一熱固性含矽聚合物之第一組成物；提供熱塑性組成物；使用增材製造裝置列印：（i）包含第一熱固性含矽聚合物之第一組成物的第一至少部分層，其使用增材製造裝置列印進行；及（ii）包含熱塑性組成物之至少部分強化層，其中將包含第一熱固性含矽聚合物之第一組成物的第一至少部分層及至少部分強化層列印在同一層內或在連續層中。In one specific example, the present invention includes a method of forming a composite article comprising a thermosetting silicon-containing polymer, the method comprising: providing a first composition comprising a first thermosetting silicon-containing polymer; providing a thermoplastic composition; using additives Manufacturing device prints: (i) a first at least partial layer comprising a first composition of a first thermoset silicon-containing polymer, which is printed using an additive manufacturing device; and (ii) at least a partial reinforcement comprising a thermoplastic composition A layer wherein the first at least partial layer of the first composition comprising the first thermosetting silicon-containing polymer and the at least partial reinforcement layer are printed within the same layer or in consecutive layers.
在該方法中，可將包含第一熱固性含矽聚合物之第一組成物的第一至少部分層列印在基板上。包含第一熱固性含矽聚合物之第一組成物的第一至少部分層及至少部分強化層可為在至少兩個連續層中列印的完整個別層。在該具體實例中，將包含第一熱固性含矽聚合物之第一組成物的第一至少部分層列印在基板上。In this method, a first at least partial layer of a first composition comprising a first thermoset silicon-containing polymer can be printed on a substrate. The first at least partial layer and the at least partial reinforcement layer of the first composition comprising the first thermosetting silicon-containing polymer may be complete individual layers printed in at least two consecutive layers. In this particular example, a first at least partial layer of a first composition including a first thermoset silicon-containing polymer is printed on the substrate.
可替代地，包含第一熱固性含矽聚合物之第一組成物的第一至少部分層及至少部分強化層可列印成在單層內。Alternatively, the first at least partial layer of the first composition comprising the first thermoset silicon-containing polymer and the at least partial reinforcement layer may be printed within a single layer.
第一熱固性含矽聚合物可包含至少一種選自以下之群的聚合物：聚矽氧烷；聚烷基矽氧烷；聚二烷基矽氧烷；及其組合或共聚物。第一熱固性含矽聚合物亦可包含至少一個選自由以下組成之群的官能基：羥基、烷基、烯基、炔基、芳基、烷氧基、烯氧基、炔氧基、芳氧基、芳基烷基、芳基烷氧基、芳基烯氧基、乙烯基、羧基、羰基、鹵素、雜環及其氟化基團及全氟化基團。The first thermoset silicon-containing polymer may comprise at least one polymer selected from the group consisting of polysiloxanes; polyalkylsiloxanes; polydialkylsiloxanes; and combinations or copolymers thereof. The first thermosetting silicon-containing polymer may also include at least one functional group selected from the group consisting of: hydroxyl, alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy base, arylalkyl, arylalkoxy, arylalkenyloxy, vinyl, carboxyl, carbonyl, halogen, heterocycle and its fluorinated groups and perfluorinated groups.
包含第一熱固性含矽聚合物之第一組成物可包含選自由以下組成之群的一種或組分：固化劑、固化催化劑、有機過氧化物、水解交聯劑、矽氧烷添加劑、超高分子量矽氧烷添加劑、澄清劑、UV吸收劑、光增白劑、顏料、著色劑、穩定劑、阻燃劑、石英、熱解二氧化矽、碳黑、氟化或全氟化聚合物添加劑及奈米二氧化矽顆粒。The first composition including the first thermosetting silicon-containing polymer may include one or a component selected from the group consisting of: curing agent, curing catalyst, organic peroxide, hydrolytic cross-linking agent, siloxane additive, ultra-high Molecular weight siloxane additives, clarifiers, UV absorbers, optical brighteners, pigments, colorants, stabilizers, flame retardants, quartz, pyrolytic silica, carbon black, fluorinated or perfluorinated polymer additives and nanosilica particles.
熱塑性組成物可包含至少一種選自由以下組成之群的熱塑性材料：聚烯烴、聚甲醛、聚醯胺、聚酯、聚醯亞胺、聚伸芳基醚、聚伸芳基醚酮、聚伸芳基醚碸、與聚苯乙烯共混之聚伸苯醚、聚丙烯腈-丁二烯-苯乙烯、聚苯乙烯-丙烯腈、聚丙烯腈、聚苯乙烯、聚對苯二甲酸乙二酯、二醇類改質聚對苯二甲酸乙二酯、熱塑性彈性體及熱塑性聚胺甲酸酯以及其共聚物、共混物、摻合物及衍生物。強化層可包含纖維。The thermoplastic composition may comprise at least one thermoplastic material selected from the group consisting of: polyolefin, polyoxymethylene, polyamide, polyester, polyimide, polyarylene ether, polyarylene ether ketone, polyamide Aryl ether esters, polyphenylene ether blended with polystyrene, polyacrylonitrile-butadiene-styrene, polystyrene-acrylonitrile, polyacrylonitrile, polystyrene, polyethylene terephthalate Ester, glycol modified polyethylene terephthalate, thermoplastic elastomers and thermoplastic polyurethanes as well as their copolymers, blends, blends and derivatives. The reinforcement layer may contain fibers.
該方法可進一步包含在列印至少部分強化層之前，將包含第一熱固性含矽聚合物之第一組成物的一或多個額外的至少部分層列印在其第一至少部分層上。The method may further comprise printing one or more additional at least partial layers of the first composition comprising the first thermosetting silicon-containing polymer on the first at least partial layer prior to printing the at least partial reinforcing layer.
該方法可進一步包含將包含熱塑性組成物之一或多個額外的至少部分強化層列印在至少部分強化層上。The method may further comprise printing one or more additional at least partially reinforced layers comprising a thermoplastic composition on the at least partially reinforced layer.
該方法可進一步包含連續且以交替方式將包含第一熱固性含矽聚合物之第一組成物的一或多個額外的至少部分層及包含熱塑性組成物之一或多個額外的至少部分強化層列印在至少一個強化層上。The method may further comprise successively and in an alternating manner one or more additional at least partial layers of the first composition comprising the first thermosetting silicon-containing polymer and one or more additional at least partially reinforced layers comprising the thermoplastic composition Print on at least one reinforcement layer.
該方法可進一步包含將藉由該方法形成之物件壓縮模製為經改質物件。The method may further include compression molding the article formed by the method into a modified article.
本發明亦包括由上文提及以及本文所述之不同方法具體實例形成的三維物件。物件可具有複合結構，該複合結構包含有包含熱固性含矽聚合物之第一組成物的至少一個至少部分層及包含熱塑性材料之強化組成物的至少一個部分層。The present invention also includes three-dimensional objects formed by various embodiments of the methods mentioned above and described herein. The article may have a composite structure comprising at least one at least partial layer of a first composition comprising a thermosetting silicon-containing polymer and at least one partial layer of a reinforcing composition comprising a thermoplastic material.
該方法可進一步包含（e）提供包含第二熱固性含矽聚合物之第二組成物；及（f）使用增材製造裝置將包含第二熱固性含矽聚合物之第二組成物的至少部分第一層列印在至少部分強化層上。The method may further comprise (e) providing a second composition comprising a second thermosetting silicon-containing polymer; and (f) using an additive manufacturing device to form at least a portion of the second composition comprising the second thermosetting silicon-containing polymer. A layer is printed on at least part of the reinforcement layer.
在此類具體實例中，包含第二熱固性含矽聚合物之第二組成物的第一至少部分層可為完整層，且至少部分強化層可為完整層。可替代地，亦可將包含第二熱固性含矽聚合物之第二組成物的第一至少部分層及至少部分強化層列印成在單層內，該單層自身可能為完整層或部分層，或在一些具體實例中為圖案化層。In such embodiments, the first at least partial layer of the second composition comprising the second thermoset silicon-containing polymer can be an integral layer, and at least a portion of the reinforcing layer can be an integral layer. Alternatively, the first at least partial layer of the second composition comprising the second thermosetting silicon-containing polymer and the at least partial reinforcing layer may be printed within a single layer, which may itself be a complete layer or a partial layer , or in some specific examples a patterned layer.
第一熱固性含矽聚合物及/或任何第二熱固性含矽聚合物可各自獨立地包含至少一種選自以下之群的聚合物：聚矽氧烷；聚烷基矽氧烷；聚二烷基矽氧烷；及其組合或共聚物。The first thermosetting silicon-containing polymer and/or any second thermosetting silicon-containing polymer may each independently comprise at least one polymer selected from the group consisting of: polysiloxane; polyalkylsiloxane; polydialkyl Siloxanes; and combinations or copolymers thereof.
第一熱固性含矽聚合物及/或第二熱固性含矽聚合物亦可獨立地包含至少一個選自由以下組成之群的官能基：羥基、烷基、烯基、炔基、芳基、烷氧基、烯氧基、炔氧基、芳氧基、芳基烷基、芳基烷氧基、芳基烯氧基、乙烯基、羧基、羰基、鹵素、雜環及其氟化基團及全氟化基團。The first thermosetting silicon-containing polymer and/or the second thermosetting silicon-containing polymer may also independently include at least one functional group selected from the group consisting of: hydroxyl, alkyl, alkenyl, alkynyl, aryl, alkoxy base, alkenyloxy, alkynyloxy, aryloxy, arylalkyl, arylalkoxy, arylalkenyloxy, vinyl, carboxyl, carbonyl, halogen, heterocycle and its fluorinated groups and all Fluorinated groups.
包含第一熱固性含矽聚合物之第一組成物及/或包含第二熱固性含矽聚合物之第二組成物可獨立地包含選自由以下組成之群的一種或組分：固化劑、固化催化劑、有機過氧化物、水解交聯劑、矽氧烷添加劑、超高分子量矽氧烷添加劑、澄清劑、UV吸收劑、光增白劑、顏料、著色劑、穩定劑、阻燃劑、石英、熱解二氧化矽、碳黑、氟化或全氟化聚合物添加劑及奈米二氧化矽顆粒。The first composition including the first thermosetting silicon-containing polymer and/or the second composition including the second thermosetting silicon-containing polymer may independently include one or a component selected from the group consisting of: curing agent, curing catalyst , organic peroxides, hydrolytic cross-linking agents, siloxane additives, ultra-high molecular weight siloxane additives, clarifiers, UV absorbers, optical brighteners, pigments, colorants, stabilizers, flame retardants, quartz, Pyrolytic silica, carbon black, fluorinated or perfluorinated polymer additives and nano-silica particles.
第一熱固性含矽聚合物及第二熱固性含矽聚合物可相同或不同。The first thermosetting silicon-containing polymer and the second thermosetting silicon-containing polymer may be the same or different.
在此具體實例中，熱塑性組成物可包含至少一種選自由以下組成之群的熱塑性材料：聚烯烴、聚甲醛、聚醯胺、聚酯、聚醯亞胺、聚伸芳基醚、聚伸芳基醚酮、聚伸芳基醚碸、與聚苯乙烯共混之聚伸苯醚、聚丙烯腈-丁二烯-苯乙烯、聚苯乙烯-丙烯腈、聚丙烯腈、聚苯乙烯、聚對苯二甲酸乙二酯、二醇類改質聚對苯二甲酸乙二酯、熱塑性彈性體及熱塑性聚胺甲酸酯以及其共聚物、共混物、摻合物及衍生物。In this specific example, the thermoplastic composition may comprise at least one thermoplastic material selected from the group consisting of: polyolefin, polyoxymethylene, polyamide, polyester, polyimide, polyarylene ether, polyarylene ether ether ketone, polyaryl ether ketone, polyphenylene ether blended with polystyrene, polyacrylonitrile-butadiene-styrene, polystyrene-acrylonitrile, polyacrylonitrile, polystyrene, poly Ethylene terephthalate, glycol-modified polyethylene terephthalate, thermoplastic elastomers and thermoplastic polyurethanes and their copolymers, blends, blends and derivatives.
該方法可進一步包含在列印至少部分強化層之前，將包含第一熱固性含矽聚合物之第一組成物的一或多個連續的至少部分層列印在其第一至少部分層上。The method may further comprise printing one or more consecutive at least partial layers of the first composition comprising the first thermosetting silicon-containing polymer on the first at least partial layer before printing at least a portion of the reinforcing layer.
該方法可進一步包含在列印包含第二熱固性含矽聚合物之第二組成物的第一至少部分層之前，列印包含熱塑性組成物之一或多個連續的至少部分強化層。The method may further comprise printing one or more consecutive at least partially reinforced layers comprising the thermoplastic composition prior to printing the first at least partial layer of the second composition comprising the second thermoset silicon-containing polymer.
該方法可進一步包含將包含第二熱固性含矽聚合物之第二組成物的一或多個連續的至少部分層列印在包含第二熱固性含矽聚合物之第二組成物的第一至少部分層上。The method may further comprise printing one or more consecutive at least partial layers of the second composition comprising the second thermoset silicon-containing polymer on the first at least portion of the second composition comprising the second thermoset silicon-containing polymer. layer.
該方法可進一步包含連續且以交替方式根據經設計圖案將包含第一熱固性含矽聚合物之第一組成物的一或多個額外的至少部分層、包含熱塑性組成物之一或多個額外的至少部分強化層及包含第二熱固性含矽聚合物之第二組成物的一或多個額外的至少部分層列印在包含第二含矽聚合物之第二組成物的第一至少部分層上。The method may further comprise applying, successively and in an alternating manner, one or more additional at least partial layers of a first composition comprising a first thermosetting silicon-containing polymer, one or more additional at least partial layers of a thermoplastic composition according to a designed pattern. The at least partial reinforcement layer and one or more additional at least partial layers of a second composition including a second thermoset silicon-containing polymer are printed on the first at least partial layer of a second composition including a second silicon-containing polymer. .
在該方法中，可將包含第一熱固性含矽聚合物之第一組成物的至少部分層中之各者、包含熱塑性組成物之至少部分強化層中之各者及包含第二熱固性含矽聚合物之第二組成物的至少部分層中之各者列印為完整層。可替代地，可將其中之一或多者單獨或與其他此類聚合物及強化層一起列印在部分層中。In this method, each of at least part of the layer of the first composition including the first thermoset silicon-containing polymer, each of at least part of the reinforced layer including the thermoplastic composition, and each of the second thermoset silicon-containing polymer may be Each of at least some of the layers of the second composition of the object is printed as a complete layer. Alternatively, one or more of these may be printed in partial layers alone or together with other such polymers and reinforcing layers.
該方法可進一步包含將藉由該方法形成之物件壓縮模製為經改質物件。The method may further include compression molding the article formed by the method into a modified article.
該方法可進一步包含重複上文提及之步驟（c）、（d）及（f）以基於電腦設計模型形成物件。該物件可包含呈管狀或圓柱狀固體物件之組態。The method may further include repeating the above-mentioned steps (c), (d) and (f) to form the object based on the computer design model. The object may include a configuration of solid objects in the form of tubular or cylindrical objects.
三維物件可藉由上文提及之方法之具體實例形成，具有第一及第二熱固性含矽聚合物，且如本文所述可具有包含由以下形成之以下至少部分層中之至少一者的複合結構：包含熱固性含矽聚合物之第一組成物、包含熱塑性材料之強化組成物及包含熱固性含矽聚合物之第二組成物。The three-dimensional object may be formed by specific examples of the methods mentioned above, having first and second thermosetting silicon-containing polymers, and as described herein may have at least one of at least a portion of the following layers formed from Composite structure: a first composition including a thermosetting silicon-containing polymer, a reinforced composition including a thermoplastic material, and a second composition including a thermosetting silicon-containing polymer.
在一個具體實例中，物件可為例如但不意欲限於O型環、密封件、密封墊、醫療裝置、醫療植入物或其零件。In one specific example, the article may be, for example, but is not intended to be limited to, an O-ring, a seal, a gasket, a medical device, a medical implant, or parts thereof.
三維物件可進一步經歷壓縮模製以形成經改質物件。The three-dimensional object may further undergo compression molding to form a modified object.
本發明進一步包括用於製備包含熱固性含矽聚合物之複合物件的設備，該設備包含：具有列印機驅動機構之增材製造列印機；用於形成第一組成物之第一至少部分層的第一列印噴嘴；及用於形成第二組成物之第二至少部分層的第二列印噴嘴，其中該增材製造列印機能夠提供第一組成物及第二組成物中之各者的兩個或更多個至少部分層以根據電腦設計模型形成第一組成物及第二組成物之三維複合物件，且其中第一列印噴嘴及第二列印噴嘴中之至少一者為加壓列印噴嘴，其包含與其可操作接觸的加熱機構。第一組成物及第二組成物可相同或不同。第一組成物可包含第一熱固性含矽聚合物，且第二組成物可包含第二熱固性含矽聚合物或熱塑性聚合物。The present invention further includes an apparatus for preparing a composite article comprising a thermoset silicon-containing polymer, the apparatus comprising: an additive manufacturing printer having a printer drive mechanism; and for forming a first at least partial layer of the first composition. a first printing nozzle; and a second printing nozzle for forming a second at least partial layer of a second composition, wherein the additive manufacturing printer is capable of providing each of the first composition and the second composition two or more at least partial layers to form a three-dimensional composite object of the first composition and the second composition according to the computer design model, and wherein at least one of the first printing nozzle and the second printing nozzle is A pressurized printing nozzle including a heating mechanism in operative contact therewith. The first component and the second component may be the same or different. The first composition can include a first thermoset silicon-containing polymer, and the second composition can include a second thermoset silicon-containing polymer or a thermoplastic polymer.
第一組成物可包含第一熱固性含矽聚合物，且第二組成物可包含第二熱固性含矽聚合物，且第一噴嘴及第二噴嘴中之各者可為加壓噴嘴。在此類具體實例中，第一熱固性含矽聚合物及第二熱固性含矽聚合物可相同。The first composition may include a first thermosetting silicon-containing polymer, and the second composition may include a second thermosetting silicon-containing polymer, and each of the first nozzle and the second nozzle may be a pressurized nozzle. In such embodiments, the first thermoset silicon-containing polymer and the second thermoset silicon-containing polymer can be the same.
該設備可包含用於形成第三組成物之第三層的第三列印噴嘴。第三組成物與第一組成物及/或第二組成物相同，或可不同。The apparatus may include a third printing nozzle for forming a third layer of a third composition. The third component is the same as the first component and/or the second component, or may be different.
列印噴嘴中之至少一者可在電腦設計模型中經可操作地程式化以根據設計圖案列印至少部分層。設計圖案中之至少部分層可為熱塑性層。第一組成物及/或第二組成物可呈長絲形式。At least one of the printing nozzles can be operatively programmed in the computer design model to print at least a portion of the layer according to the design pattern. At least some of the layers in the design may be thermoplastic layers. The first component and/or the second component may be in the form of filaments.
第一噴嘴及第二噴嘴可為噴嘴整件之一部分，該噴嘴整件進一步包括用於將第一噴嘴及第二噴嘴穩定固定在適當位置以進行串聯操作的安裝臂。安裝臂可具有用於支撐第二噴嘴的橫向延伸之支撐部分及具有自其穿過以支撐第一噴嘴之開口的底座支撐部分。The first nozzle and the second nozzle may be part of a nozzle unit, the nozzle unit further comprising a mounting arm for stably fixing the first nozzle and the second nozzle in position for tandem operation. The mounting arm may have a laterally extending support portion for supporting the second nozzle and a base support portion having an opening therethrough for supporting the first nozzle.
噴嘴整件可進一步包含噴嘴整件列印機驅動機構。第一噴嘴可為高壓活塞擠壓機。第一噴嘴可與加壓源連通。第一噴嘴加熱帶可具有噴嘴端部分及加熱帶，該加熱帶經調適以圍繞噴嘴端部分安置以用於在具有熱固性含矽聚合物之組成物藉由噴嘴列印時加熱該組成物。The nozzle unit may further include a nozzle unit printer drive mechanism. The first nozzle may be a high pressure piston extruder. The first nozzle may be in communication with a pressurized source. The first nozzle heating belt may have a nozzle end portion and a heating belt adapted to be positioned around the nozzle end portion for heating a composition having a thermosetting silicon-containing polymer as the composition is printed through the nozzle.
第二噴嘴可為熱塑性材料噴嘴擠壓機。第二噴嘴可為纖維噴嘴擠壓機。The second nozzle may be a thermoplastic material nozzle extruder. The second nozzle may be a fiber nozzle extruder.
在本文之又一具體實例中，本發明包括一種形成包含熱固性含矽聚合物及長強化纖維之複合物件之方法，其包含：提供包含第一熱固性含矽聚合物之第一組成物；提供連續長強化纖維；使用增材製造裝置之第一噴嘴列印包含第一熱固性含矽聚合物之第一組成物的至少部分層；及使用增材製造裝置之第二噴嘴列印長強化纖維之至少部分層，其中將包含第一熱固性含矽聚合物之第一組成物的至少部分層及長強化纖維之至少部分層列印在同一層內或在連續層中。In yet another embodiment herein, the invention includes a method of forming a composite article comprising a thermosetting silicon-containing polymer and long reinforcing fibers, comprising: providing a first composition comprising a first thermosetting silicon-containing polymer; providing a continuous long reinforcing fibers; printing at least a partial layer of the first composition comprising a first thermosetting silicon-containing polymer using a first nozzle of an additive manufacturing device; and printing at least a portion of the long reinforcing fibers using a second nozzle of an additive manufacturing device Partial layers, wherein at least part of the layer of the first composition including the first thermosetting silicon-containing polymer and at least part of the layer of long reinforcing fibers are printed in the same layer or in consecutive layers.
可將包含第一熱固性含矽聚合物之第一組成物的至少部分層列印在基板上。包含第一熱固性含矽聚合物之第一組成物的至少部分層及長強化纖維之至少部分層可為在至少兩個連續層中列印的完整個別層，或一者可為完整的且另一者為部分的，或反之亦然。包含第一熱固性含矽聚合物之第一組成物的至少部分層及長強化纖維之至少部分層可進一步列印成在單層內。At least a portion of the layer of the first composition including the first thermoset silicon-containing polymer can be printed on the substrate. At least part of the layer of the first composition comprising the first thermosetting silicon-containing polymer and at least part of the layer of long reinforcing fibers may be complete individual layers printed in at least two consecutive layers, or one may be complete and the other One is partial, or vice versa. At least part of the layer of the first composition including the first thermoset silicon-containing polymer and at least part of the layer of long reinforcing fibers may be further printed within a single layer.
第一熱固性含矽聚合物可包含至少一種選自以下之群的聚合物：聚矽氧烷；聚烷基矽氧烷；聚二烷基矽氧烷；及其組合或共聚物。第一熱固性含矽聚合物亦可包含至少一個選自由以下組成之群的官能基：羥基、烷基、烯基、炔基、芳基、烷氧基、烯氧基、炔氧基、芳氧基、芳基烷基、芳基烷氧基、芳基烯氧基、乙烯基、羧基、羰基、鹵素、雜環及其氟化基團及全氟化基團。包含第一熱固性含矽聚合物之第一組成物亦可包含選自由以下組成之群的一或多種組分：固化劑、固化催化劑、有機過氧化物、水解交聯劑、矽氧烷添加劑、超高分子量矽氧烷添加劑、澄清劑、UV吸收劑、光增白劑、顏料、著色劑、穩定劑、阻燃劑、石英、熱解二氧化矽、碳黑、氟化或全氟化聚合物添加劑及奈米二氧化矽顆粒。The first thermoset silicon-containing polymer may comprise at least one polymer selected from the group consisting of polysiloxanes; polyalkylsiloxanes; polydialkylsiloxanes; and combinations or copolymers thereof. The first thermosetting silicon-containing polymer may also include at least one functional group selected from the group consisting of: hydroxyl, alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy base, arylalkyl, arylalkoxy, arylalkenyloxy, vinyl, carboxyl, carbonyl, halogen, heterocycle and its fluorinated groups and perfluorinated groups. The first composition including the first thermosetting silicon-containing polymer may also include one or more components selected from the group consisting of: curing agent, curing catalyst, organic peroxide, hydrolytic cross-linking agent, siloxane additive, Ultra-high molecular weight siloxane additives, clarifiers, UV absorbers, optical brighteners, pigments, colorants, stabilizers, flame retardants, quartz, pyrolytic silica, carbon black, fluorinated or perfluorinated polymerization additives and nano-silica particles.
提供給該方法之長連續強化纖維及/或所得物件中之長強化纖維可選自由以下組成之群：碳纖維、玻璃纖維、硼纖維、氧化鋁纖維、碳化矽纖維、石英纖維、醯胺纖維、聚苯并唑纖維、超高分子量聚乙烯纖維、聚丙烯、聚對苯二甲酸乙二酯、聚乙烯、聚醯亞胺、聚芳酯、聚醚醯亞胺、聚乙烯醇、嫘縈、聚丙烯腈纖維以及天然及合成纖維共混物。在另一具體實例中，長強化纖維可為選自由以下組成之群的天然纖維：角蛋白、亞麻、黏液、劍麻、***及黃麻。長強化纖維較佳選自由以下組成之群：碳纖維、醯胺纖維及玻璃纖維。長強化纖維亦可提供為單一纖維、纖維絲束、纖維束、編織物、纖維之共混物中之一者或提供為混合纖維束。The long continuous reinforcing fibers provided to the method and/or the long reinforcing fibers in the resulting article may be selected from the group consisting of: carbon fiber, glass fiber, boron fiber, alumina fiber, silicon carbide fiber, quartz fiber, amide fiber, polybenzo Azole fiber, ultra-high molecular weight polyethylene fiber, polypropylene, polyethylene terephthalate, polyethylene, polyimide, polyarylate, polyetherimide, polyvinyl alcohol, rayon, polyacrylonitrile Fibers and natural and synthetic fiber blends. In another specific example, the long reinforcing fibers may be natural fibers selected from the group consisting of keratin, flax, mucilage, sisal, hemp, and jute. The long reinforcing fibers are preferably selected from the group consisting of carbon fibers, amide fibers and glass fibers. The long reinforcing fibers may also be provided as one of single fibers, fiber tows, fiber tows, braids, blends of fibers or as mixed fiber tows.
該方法可進一步包含在纖維離開第二噴嘴時使用纖維切割裝置切割長連續纖維。The method may further comprise using a fiber cutting device to cut the long continuous fiber as the fiber exits the second nozzle.
使用第一噴嘴列印第一熱固性含矽聚合物可進一步包含加熱增材製造裝置之第一噴嘴。此外，使用第二噴嘴列印長強化纖維可進一步包含加熱第二噴嘴。該方法可進一步包含在第二噴嘴中在長強化纖維上方共擠壓包含可擠壓聚合材料之組成物。在此類具體實例中，可擠壓聚合材料可為熱塑性組成物或包含第二熱固性含矽聚合物之第二組成物。第一熱固性含矽聚合物可與第二熱固性含矽聚合物相同或不同。可擠壓聚合材料亦可為熱塑性組成物，其包含至少一種選自例如由以下組成之群的熱塑性材料：聚烯烴、聚甲醛、聚醯胺、聚酯、聚醯亞胺、聚伸芳基醚、聚伸芳基醚酮、聚伸芳基醚碸、與聚苯乙烯共混之聚伸苯醚、聚丙烯腈-丁二烯-苯乙烯、聚苯乙烯-丙烯腈、聚丙烯腈、聚苯乙烯、聚對苯二甲酸乙二酯、二醇類改質聚對苯二甲酸乙二酯、熱塑性彈性體及熱塑性聚胺甲酸酯以及其共聚物、共混物、摻合物及衍生物。包含可擠壓聚合材料之組成物可包含一或多種強化纖維，諸如短纖維或短切纖維、奈米管、碳奈米結構或鬚晶。包含第一熱固性含矽聚合物之第一組成物亦可包含此類額外強化纖維。Printing the first thermosetting silicon-containing polymer using the first nozzle may further include heating the first nozzle of the additive manufacturing device. In addition, printing the long reinforcing fibers using the second nozzle may further include heating the second nozzle. The method may further comprise co-extruding a composition comprising the extrudable polymeric material over the long reinforcing fibers in the second nozzle. In such embodiments, the extrudable polymeric material may be a thermoplastic composition or a second composition including a second thermoset silicon-containing polymer. The first thermoset silicon-containing polymer may be the same as or different from the second thermoset silicon-containing polymer. The extrudable polymeric material may also be a thermoplastic composition comprising at least one thermoplastic material selected from, for example, the group consisting of: polyolefins, polyoxymethylene, polyamides, polyesters, polyimides, polyarylenes Ether, polyarylene ether ketone, polyarylene ether ketone, polyphenylene ether blended with polystyrene, polyacrylonitrile-butadiene-styrene, polystyrene-acrylonitrile, polyacrylonitrile, Polystyrene, polyethylene terephthalate, glycol-modified polyethylene terephthalate, thermoplastic elastomers and thermoplastic polyurethanes and their copolymers, blends, blends and derivative. Compositions containing extrudable polymeric materials may include one or more reinforcing fibers, such as short or chopped fibers, nanotubes, carbon nanostructures, or whiskers. The first composition including the first thermoset silicon-containing polymer may also include such additional reinforcing fibers.
該方法可進一步包含在列印長強化纖維之至少部分層之前或之後在其至少部分層上列印包含第一熱固性含矽聚合物之第一組成物的一或多個額外的至少部分層。該方法亦可進一步包含列印長強化纖維之一或多個額外的至少部分層。該方法亦可進一步包含連續且以交替方式列印包含第一熱固性含矽聚合物之第一組成物的一或多個額外的至少部分層及長強化纖維之一或多個額外的至少部分層，其中長強化纖維可視情況具有擠壓於其上之共擠壓材料組成物，例如包含如上文提及之熱塑性材料的共擠壓材料組成物。The method may further comprise printing one or more additional at least partial layers of the first composition comprising the first thermosetting silicon-containing polymer on the at least partial layers before or after printing the at least partial layers of the long reinforcing fibers. The method may further comprise printing one or more additional at least partial layers of long reinforcing fibers. The method may further comprise printing one or more additional at least partial layers of a first composition comprising a first thermosetting silicon-containing polymer and one or more additional at least partial layers of long reinforcing fibers in a continuous and alternating manner. , wherein the long reinforcing fibers optionally have a co-extruded material composition extruded thereon, for example a co-extruded material composition including a thermoplastic material as mentioned above.
該方法亦可進一步包含在大體上橫向方向上列印包含第一熱固性含矽聚合物之第一組成物的至少部分層及在第二大體上縱向方向上列印長強化纖維之至少部分層。此圖案亦可顛倒，其中包含第一熱固性含矽聚合物之第一組成物在大體上縱向方向上列印，且長強化纖維在大體上橫向方向上列印。The method may further comprise printing at least a partial layer of the first composition comprising a first thermosetting silicon-containing polymer in a generally transverse direction and printing at least a partial layer of the long reinforcing fibers in a second generally longitudinal direction. This pattern can also be reversed, with the first composition including the first thermoset silicon-containing polymer printing in a generally longitudinal direction and the long reinforcing fibers printing in a generally transverse direction.
該方法亦可進一步包含將藉由該方法形成之複合物件壓縮模製為經改質複合物件。The method may further include compression molding the composite object formed by the method into a modified composite object.
在另一具體實例中，本發明亦包括由本文提及之方法之具體實例形成的三維複合物件，其具有複合結構，該複合結構包含包括熱固性含矽聚合物之第一組成物的至少部分層中之至少一者及長強化纖維之至少一個部分層中之至少一者。此類三維物件可為O型環、密封件、密封墊、醫療裝置、醫療植入物或其零件或如本文提及之各種其他物品。In another embodiment, the present invention also includes a three-dimensional composite article formed by embodiments of the methods mentioned herein, having a composite structure including at least partial layers of a first composition including a thermoset silicon-containing polymer. and at least one of at least one partial layer of long reinforcing fibers. Such three-dimensional objects may be O-rings, seals, gaskets, medical devices, medical implants or parts thereof, or various other items as mentioned herein.
上文在另一具體實例中提及之方法可進一步包含（e）提供包含第二熱固性含矽聚合物之第二組成物；及（f）使用增材製造裝置在長強化纖維之至少部分層上列印包含第二熱固性含矽聚合物之第二組成物的至少部分第一層。包含第二熱固性含矽聚合物之第二組成物可藉由經由第一噴嘴交替引入、藉由在長強化纖維上方共擠壓該材料及/或藉由使用專用於引入包含第二熱固性含矽聚合物之第二組成物的第三安裝噴嘴。在此類方法具體實例中，包含第二熱固性含矽聚合物之第二組成物的第一至少部分層可為完整層。此外，第一熱固性含矽聚合物及第二熱固性含矽聚合物可彼此相同或不同。The method mentioned above in another embodiment may further comprise (e) providing a second composition comprising a second thermosetting silicon-containing polymer; and (f) using an additive manufacturing device to fabricate at least part of the layer of long reinforcing fibers. At least a portion of the first layer of a second composition including a second thermosetting silicon-containing polymer is printed thereon. The second composition comprising the second thermoset silicon-containing polymer may be introduced by alternating through the first nozzle, by co-extruding the material over the long reinforcing fibers, and/or by using a polymer specifically designed to introduce the second thermoset silicon-containing polymer. A third installed nozzle of the second composition of polymer. In such method embodiments, the first at least partial layer of the second composition comprising the second thermoset silicon-containing polymer may be a complete layer. Furthermore, the first thermosetting silicon-containing polymer and the second thermosetting silicon-containing polymer may be the same as or different from each other.
該方法可進一步包含重複步驟（c）、（d）及（f）以基於電腦設計模型形成物件。The method may further include repeating steps (c), (d) and (f) to form the object based on the computer design model.
該方法可進一步包含根據經設計圖案列印包含第一熱固性含矽聚合物之第一組成物的一或多個額外的至少部分層及長強化纖維之一或多個額外的至少部分層。The method may further comprise printing one or more additional at least partial layers of the first composition including the first thermoset silicon-containing polymer and one or more additional at least partial layers of long reinforcing fibers according to the designed pattern.
上文提及之具體實例中之方法亦可進一步包含列印包含第二熱固性含矽聚合物之第二組成物的一或多個額外的至少部分層。The methods of the embodiments mentioned above may further comprise printing one or more additional at least partial layers of the second composition comprising the second thermosetting silicon-containing polymer.
上文提及之具體實例中之方法可進一步包含重複步驟（c）及（d）以基於電腦設計模型形成物件。The method in the specific example mentioned above may further include repeating steps (c) and (d) to form the object based on the computer design model.
在又一具體實例中，本發明進一步包括用於製備包含熱固性含矽聚合物及長連續纖維之複合物件的設備，其包含：具有列印機驅動機構之增材製造列印機、用於形成第一組成物之至少部分層的第一噴嘴；及用於形成長強化纖維之至少部分層的第二噴嘴、經安置用於切割離開第二噴嘴之長強化纖維的纖維切割裝置，其中增材製造列印機能夠提供第一組成物中之各者的一或多個至少部分層及長強化纖維之至少部分層中之一或多者，以根據電腦設計模型形成第一組成物及長強化纖維之三維複合物件，且其中第一噴嘴及第二噴嘴中之至少一者為加壓列印噴嘴，其包含與其可操作接觸的加熱機構。In yet another specific example, the invention further includes an apparatus for preparing a composite article comprising a thermosetting silicon-containing polymer and long continuous fibers, comprising: an additive manufacturing printer having a printer drive mechanism, for forming a first nozzle for forming at least a partial layer of the first composition; and a second nozzle for forming at least a partial layer of long reinforcing fibers, a fiber cutting device positioned for cutting the long reinforcing fibers exiting the second nozzle, wherein the additive The manufacturing printer is capable of providing one or more at least partial layers of each of the first composition and at least partial layers of long reinforcement fibers to form the first composition and the long reinforcement according to the computer design model A three-dimensional composite object of fibers, wherein at least one of the first nozzle and the second nozzle is a pressurized printing nozzle, including a heating mechanism in operative contact therewith.
在該設備中，在第一噴嘴中，第一組成物可包含第一熱固性含矽聚合物。該設備可進一步包含用於形成第二組成物之第三層的第三噴嘴，其中第二組成物可包含可擠壓聚合材料。In the apparatus, in the first nozzle, the first composition may comprise a first thermosetting silicon-containing polymer. The apparatus may further comprise a third nozzle for forming a third layer of a second composition, wherein the second composition may comprise an extrudable polymeric material.
第一噴嘴及第二噴嘴可經組態以便在操作時經加熱。第二噴嘴可經組態以能夠在長強化纖維上方共擠壓可擠壓聚合材料。The first nozzle and the second nozzle may be configured to be heated during operation. The second nozzle can be configured to co-extrude the extrudable polymeric material over the long reinforcing fibers.
第一噴嘴及第二噴嘴中之至少一者可在電腦設計模型中經可操作地程式化以列印設計圖案中之至少部分層。第一噴嘴及第二噴嘴較佳均在電腦設計模型中可操作地程式化以列印設計圖案中之第一組成物及長強化纖維的至少部分層。At least one of the first nozzle and the second nozzle can be operatively programmed in the computer design model to print at least a portion of the layer in the design pattern. Preferably, both the first nozzle and the second nozzle are operatively programmed in the computer design model to print at least partial layers of the first composition and long reinforcing fibers in the design pattern.
該設備可經組態以使得第一組成物可以長絲形式提供。第一噴嘴及第二噴嘴可為噴嘴整件之一部分，該噴嘴整件進一步包括用於將第一噴嘴及第二噴嘴穩定固定在適當位置以進行串聯操作的安裝臂。安裝臂可具有用於支撐第一噴嘴及第二噴嘴之支撐座，且較佳可操作地且可拆卸地連接至纖維切割裝置，其中支撐座可進一步具有穿過其的各別開口以支撐第一噴嘴及第二噴嘴。The apparatus may be configured such that the first composition is provided in filament form. The first nozzle and the second nozzle may be part of a nozzle unit, the nozzle unit further comprising a mounting arm for stably fixing the first nozzle and the second nozzle in position for tandem operation. The mounting arm may have a support base for supporting the first nozzle and the second nozzle, and preferably is operably and removably connected to the fiber cutting device, wherein the support base may further have respective openings therethrough for supporting the second nozzle. A nozzle and a second nozzle.
第一噴嘴可為高壓活塞擠壓機。此類具體實例中之第一噴嘴較佳與加壓源連通。The first nozzle may be a high pressure piston extruder. The first nozzle in such embodiments is preferably in communication with a pressurized source.
第一噴嘴加熱帶可具有噴嘴端部分，該噴嘴端部分具有加熱帶，該加熱帶經調適以圍繞噴嘴端部分安置以用於在具有熱固性含矽聚合物之組成物藉由噴嘴列印時加熱該組成物。第二噴嘴可為長強化纖維擠壓機。第二噴嘴亦可經組態以接收可擠壓聚合材料以在長強化纖維上方共擠壓。纖維切割裝置較佳可操作以在列印長強化纖維之至少部分層時以受控間隔長度連續切割長強化纖維。第二噴嘴可具有噴嘴端部分及經調適以圍繞噴嘴端部分安置以用於加熱長強化纖維的加熱帶。The first nozzle heating band may have a nozzle end portion having a heating band adapted to be disposed about the nozzle end portion for heating a composition having a thermosetting silicon-containing polymer as it is printed by the nozzle the composition. The second nozzle may be a long reinforcing fiber extruder. The second nozzle may also be configured to receive extrudable polymeric material for co-extrusion over the long reinforcing fibers. The fiber cutting device is preferably operable to continuously cut the long reinforcing fibers at controlled spaced lengths while printing at least part of the layer of long reinforcing fibers. The second nozzle may have a nozzle end portion and a heating tape adapted to be positioned around the nozzle end portion for heating the long reinforcing fibers.
本發明包括形成利用增材製造形成之複合三維彈性體物件，包括包含熱固性含矽聚合物之複合物的方法及設備。複合物亦可包括熱塑性材料之強化層。The present invention includes methods and apparatus for forming composite three-dimensional elastomeric articles formed using additive manufacturing, including composites including thermoset silicon-containing polymers. The composite may also include a reinforced layer of thermoplastic material.
在本文中之描述中，除非另外規定，否則如「內（inner）」及「外（outer）」、「向上（upwardly）」及「向下（downwardly）」、「向內（inwardly）」及「向外（outwardly）」、「右（right）」及「左（left）」、「上（upper）」及「下（lower）」、「遠端（distal）」及「近端（proximal）」之詞語及類似意思之詞語係指用於幫助闡明本發明之特點的圖式中之方向。In the descriptions herein, unless otherwise specified, terms such as "inner" and "outer", "upwardly" and "downwardly", "inwardly" and "outwardly", "right" and "left", "upper" and "lower", "distal" and "proximal" The words "" and words of similar meaning refer to directions in the drawings used to help explain the features of the invention.
如本文所用，「熱固性含矽聚合物（thermoset silicon-containing polymer）」可為可固化以形成聚矽氧烷彈性體（亦稱為聚矽氧烷橡膠）之多種聚矽氧烷均聚物及共聚物中之任一者。聚矽氧烷一般為在其化學結構中併入至少矽、氧及氫之聚合物。可用於形成聚矽氧烷彈性體之可固化熱固性含矽聚合物（聚矽氧烷）包括具有主鏈之聚合物，其由ASTM國際（ASTM International）提供之標準橡膠命名定義（Standard Rubber Nomenclature definitions）在ASTM D1418-17中分類為VMQ（聚矽氧烷）、PVMQ（苯基聚矽氧烷）及FVMQ（氟聚矽氧烷）。然而，亦可使用不容易由ASTM D1418-17分類之聚矽氧烷，其限制條件為其展現如本文所述之有用的增材製造可列印特徵。As used herein, "thermoset silicon-containing polymer" can refer to a variety of polysiloxane homopolymers that can be cured to form polysiloxane elastomers (also known as polysiloxane rubbers) and Any of the copolymers. Polysiloxanes are generally polymers that incorporate at least silicon, oxygen and hydrogen into their chemical structure. Curable thermoset silicon-containing polymers (polysiloxanes) useful in forming polysiloxane elastomers include polymers having backbones according to the Standard Rubber Nomenclature definitions provided by ASTM International ) is classified into VMQ (polysiloxane), PVMQ (phenyl polysiloxane) and FVMQ (fluoropolysiloxane) in ASTM D1418-17. However, polysiloxanes that are not readily classified by ASTM D1418-17 may also be used, subject to the proviso that they exhibit useful additive manufacturing printable characteristics as described herein.
如本文所用之「固化（Curing）」意欲涵蓋藉由硫化、化學交聯、催化交聯及其類似方式向聚矽氧烷提供彈性結構之任何方法。在固化之後，熱固性含矽聚合物（聚矽氧烷）形成聚矽氧烷彈性體。如本文所用之「彈性體（elastomer）」（有時亦稱為橡膠）意欲意謂具有黏彈性特性，且在施加應力時會變形，但在移除應力之後將恢復其初始形式之一部分的聚合材料。材料恢復其初始形式之程度為彈性體特性，該特性經由其「壓縮形變（compression set）」阻力（在移除應力時不恢復的彈性體之百分比，因此壓縮形變阻力之百分比愈低，彈性恢復愈強）量測。典型地經量測之其他彈性體特性包括斷裂伸長率、楊氏模數（Young's modulus）、拉伸模數、黏度及其他物理特性。彈性體之熱行為及其固化系統對該等特性之影響亦適用於評估用於不同最終用途應用之彈性體。"Curing" as used herein is intended to encompass any method of providing an elastic structure to polysiloxane by vulcanization, chemical cross-linking, catalytic cross-linking and the like. After curing, the thermoset silicon-containing polymer (polysiloxane) forms a polysiloxane elastomer. As used herein, "elastomer" (sometimes also called rubber) is intended to mean a polymer that has viscoelastic properties and deforms when stress is applied, but will return to a portion of its original form after the stress is removed. Material. The extent to which a material returns to its original form is an elastomeric property, which is determined by its "compression set" resistance (the percentage of the elastomer that does not recover when stress is removed, so the lower the compression set resistance, the greater the elastic recovery. The stronger) measurement. Other elastomer properties that are typically measured include elongation at break, Young's modulus, tensile modulus, viscosity, and other physical properties. The thermal behavior of elastomers and the effect of their cure systems on these properties is also applicable to the evaluation of elastomers for different end-use applications.
在增材製造中，熱行為、流動性及黏度均為必須評估之特性，因為聚矽氧烷將視熱特性而不同地表現，包括列印期間的其玻璃轉移溫度（Tg）、其固化速度及其固化狀態。因為大部分聚矽氧烷彈性體本質上為熱固性的，所以其更難以用於熱塑性塑膠更容易地使用及經濟上可行的應用中。因此，此項技術中仍需要在本文中解決的在增材列印中使用聚矽氧烷彈性體的方法。In additive manufacturing, thermal behavior, flow and viscosity are all properties that must be evaluated, as polysiloxane will behave differently depending on its thermal properties, including its glass transition temperature (Tg) during printing, its cure rate and its cured state. Because most silicone elastomers are thermosets in nature, they are more difficult to use in applications where thermoplastics are more readily available and economically viable. Therefore, there is still a need in the art for methods to use polysiloxane elastomers in additive printing, which are addressed in this article.
在未固化狀態下，聚矽氧烷典型地為液體或黏著劑凝膠。用於形成聚矽氧烷橡膠之聚矽氧烷可使用多種固化系統固化，該等固化系統包括催化劑固化系統，典型地使用基於鉑之催化劑、縮合固化系統、過氧化物固化系統及肟固化系統。In the uncured state, polysiloxane is typically a liquid or adhesive gel. Polysiloxanes used to form silicone rubbers can be cured using a variety of cure systems, including catalyst cure systems, typically using platinum-based catalysts, condensation cure systems, peroxide cure systems, and oxime cure systems .
在鉑催化劑固化中，交聯使用官能性聚矽氧烷聚合物，諸如經由加成反應形成交聯之乙烯基官能性聚矽氧烷及氫化物官能性聚矽氧烷形成。該反應未留下副產物，且因此為此項技術中之固化的較佳途徑。In platinum catalyst curing, crosslinks are formed using functional polysiloxane polymers such as vinyl functional polysiloxanes and hydride functional polysiloxanes that form crosslinks via addition reactions. This reaction leaves no by-products and is therefore the preferred route to curing in this technology.
縮合系統典型地涉及以某一方式活化之交聯材料。在常見的單組分系統中，採用官能性聚矽氧烷，其在室溫下與水接觸時將經歷水解，且可水解基團（羥基或矽烷醇基團）將引發固化反應。水解反應一旦引發則繼續直至固化完成，且可在室溫下進行。縮合系統包括之交聯材料包括具有活性含氧基團（諸如烷氧基、乙醯氧基、酯基、烯氧基或肟矽烷）之官能性矽烷，例如甲基三甲氧基矽烷、甲基三乙醯氧基矽烷及類似材料。視需要，亦可使用有機金屬催化劑，諸如四烷氧基鈦酸鹽、螯合鈦酸鹽、錫催化劑（例如二月桂酸二丁錫及乙醯氧錫）催化該等經取代之基團及/或官能化基團。Condensation systems typically involve cross-linked materials that are activated in some manner. In common one-component systems, functional polysiloxanes are used, which undergo hydrolysis when in contact with water at room temperature, and hydrolyzable groups (hydroxyl or silanol groups) initiate the curing reaction. Once initiated, the hydrolysis reaction continues until curing is complete and can be carried out at room temperature. Condensation systems include cross-linking materials including functional silanes with reactive oxygen-containing groups such as alkoxy, acetyloxy, ester, alkenyloxy or oxime silane, for example methyltrimethoxysilane, methyl Triethyloxysilane and similar materials. If necessary, organic metal catalysts, such as tetraalkoxy titanates, chelated titanates, and tin catalysts (such as dibutyltin dilaurate and tin acetyl oxide) can also be used to catalyze these substituted groups and /or functional groups.
在雙組分縮合中，交聯材料及任何催化劑保留在一個容器中，而可固化聚矽氧烷聚合物組成物（不存在彼等材料）保留在單獨的容器中。在兩個容器中混合材料時引發固化。In a two-component condensation, the cross-linking material and any catalyst remain in one vessel, while the curable polysiloxane polymer composition (without those materials present) remains in a separate vessel. Curing is initiated when materials are mixed in two containers.
用於形成聚矽氧烷彈性體之其他聚矽氧烷固化系統包括過氧化物固化系統，其可經由反應性聚矽氧烷位點交聯，在聚矽氧烷鏈之間形成Si-R-Si連接。Other silicone cure systems used to form silicone elastomers include peroxide cure systems, which can cross-link via reactive silicone sites to form Si-R between silicone chains. -Si connection.
該等系統為此項技術中所熟知，且可在本文中採用在固化時使用已知或待開發之該等系統的任何聚矽氧烷，其限制條件為可固化材料能夠在增材製造列印製程期間展現賓漢塑膠行為（Bingham plastic behavior）。亦即，聚矽氧烷必須為可流動的，且固化經由速度、溫度及材料特性控制以允許聚矽氧烷可流動通過該設備，從而在變得過於黏稠以致於無法處理之前及時地列印層。賓漢塑膠為黏塑性材料，其在施加一定水平之應力且其變為黏性流體可流動之前一直保持為固體。此類材料在低於臨界值τ 0之剪應力τ下為彈性固體。一旦剪應力超過臨界剪應力（在此項技術中亦稱作「屈服應力（yield stress）」），則材料以此方式流動使得剪切速率∂ u/∂ y與所施加之剪應力超過屈服應力的量成正比，且以下方程式適用： Such systems are well known in the art, and any polysiloxane that uses such systems known or yet to be developed upon curing can be employed herein, with the proviso that the curable material can be used in additive manufacturing processes. Exhibits Bingham plastic behavior during the printing process. That is, the polysiloxane must be flowable, and curing is controlled by speed, temperature, and material properties to allow the polysiloxane to flow through the device to print in a timely manner before becoming too viscous to handle. layer. Bingham plastic is a viscoplastic material that remains solid until a certain level of stress is applied and it becomes a viscous fluid that can flow. Such materials are elastic solids under shear stress τ below a critical value τ 0 . Once the shear stress exceeds the critical shear stress (also called the "yield stress" in the art), the material flows in such a way that the shear rate ∂ u /∂ y and the applied shear stress exceed the yield stress. is directly proportional to the quantity, and the following equation applies:
若該等特性可藉由可固化聚矽氧烷達成，則此類聚矽氧烷可用於增材製造方法中，且亦使用本文中之設備進行列印。各種聚矽氧烷特性可展現該等特性及/或可諸如藉由使用添加劑進行改質以展現所要賓漢塑膠行為。If these properties can be achieved by curable polysiloxanes, such polysiloxanes can be used in additive manufacturing methods and also printed using the equipment described herein. Various polysiloxane properties may exhibit these properties and/or may be modified, such as by the use of additives, to exhibit desired Bingham plastic behaviors.
較佳地，本文所用之聚矽氧烷聚合物為以下中之一或多者：聚矽氧烷、聚烷基矽氧烷、聚二烷基矽氧烷、聚芳基矽氧烷、聚芳烷基矽氧烷及此等材料彼此或與如本文所述之熱塑性材料之共混物、摻合物或共聚物。此外，該等熱固性含矽聚合物可在經一或多個基團取代之主鏈中之矽原子上具有一或多個氫或具有一或矽鍵結鍵結基團，該等經取代之基團中之各者可進一步經官能化或進一步經取代。該等經取代之基團或官能基可為分支鏈及/或直鏈基團，包括但不限於羥基、烷基、烯基、炔基、芳基、烷氧基、烯氧基、炔氧基、芳氧基、芳基烷基、芳基烷氧基、芳基烯氧基、乙烯基、羧基、羰基、鹵素、雜環及氟化基團或全氟化基團。Preferably, the polysiloxane polymer used herein is one or more of the following: polysiloxane, polyalkylsiloxane, polydialkylsiloxane, polyarylsiloxane, polysiloxane. Aralkylsiloxanes and blends, blends or copolymers of these materials with each other or with thermoplastic materials as described herein. In addition, the thermosetting silicon-containing polymers may have one or more hydrogens on the silicon atoms in the main chain substituted by one or more groups or have one or silicon-bonded bonding groups. Each of the groups may be further functionalized or further substituted. These substituted groups or functional groups may be branched chain and/or linear groups, including but not limited to hydroxyl, alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyloxy group, vinyl group, carboxyl group, carbonyl group, halogen, heterocyclic and fluorinated group or perfluorinated group.
包括本文中之含聚矽氧烷聚合物的組成物可包括固化劑、固化引發劑、交聯劑（諸如水解交聯劑）、固化催化劑（諸如有機過氧化物）及如上文所提及且如此項技術中已知或待開發之其他固化系統組分。可進一步將添加劑及/或改質劑併入包括含聚矽氧烷聚合物之組成物中，該等添加劑及/或改質劑諸如但不限於矽氧烷添加劑、超高分子量矽氧烷添加劑、澄清劑、處理助劑、穩定劑、搖變劑、流變劑、相容劑、著色劑（諸如顏料及染料）、填料（諸如碳黑、石英、二氧化矽、熱解二氧化矽、碳奈米管、玻璃纖維）及視情況存在之偶合劑、醯胺纖維、烯烴纖維、碳纖維、UV吸收劑、UV穩定劑、潤滑劑（諸如蠟、脂肪酸）及其他流變添加劑、阻燃劑、多元醇、醯胺、氟聚合物、氟化或全氟化聚合物添加劑、奈米二氧化矽（nanosilica）（亦即奈米二氧化矽（nanosilicon dioxide））顆粒、聚矽氧烷、防黏連助劑（諸如二氧化矽及滑石）、光增白劑、分散劑、濕潤劑、相容劑及對於提供所要組成物特性已知或待開發之任何其他適合的含矽聚合物添加劑及/或改質劑，其限制條件為此類添加劑不阻止、防止或實質上阻礙藉由增材製造列印具有熱固性含矽聚合物之組成物的能力。Compositions including the polysiloxane-containing polymers herein may include a curing agent, a curing initiator, a cross-linking agent (such as a hydrolytic cross-linking agent), a curing catalyst (such as an organic peroxide), and as mentioned above and Other curing system components are known in the art or are yet to be developed. Additives and/or modifiers may further be incorporated into compositions including polysiloxane-containing polymers, such additives and/or modifiers such as, but not limited to, siloxane additives, ultra-high molecular weight siloxane additives , clarifiers, processing aids, stabilizers, thixotropic agents, rheological agents, compatibilizers, colorants (such as pigments and dyes), fillers (such as carbon black, quartz, silica, fumed silica, Carbon nanotubes, glass fibers) and optional coupling agents, amide fibers, olefin fibers, carbon fibers, UV absorbers, UV stabilizers, lubricants (such as waxes, fatty acids) and other rheological additives, flame retardants , polyols, amide, fluoropolymers, fluorinated or perfluorinated polymer additives, nanosilica (also known as nanosilica (nanosilicon dioxide)) particles, polysiloxane, anti- Adhesion aids (such as silica and talc), optical brighteners, dispersants, wetting agents, compatibilizers and any other suitable silicon-containing polymer additives known or to be developed that are necessary to provide the desired composition properties, and or modifiers, with the proviso that such additives do not prevent, prevent or substantially impede the ability to print compositions with thermoset silicon-containing polymers by additive manufacturing.
用於本文中之熱固性含矽聚合物組成物之較佳添加劑為固化劑，諸如過氧化物固化劑，其典型地以每100份聚矽氧烷聚合物約0.5至約5.5份併入，或在其他系統中為鉑催化劑，其量為每100份含矽聚合物約0.0005至約0.0015份。其他較佳添加劑包括著色劑及顏料，諸如白色（氧化鈦）、黃色（氧化鐵或偶氮鐵）、藍色（酞青素（phthalocyanine）GS或群青（ultramarine））及/或綠色（酞青素BS），其量可能變化，但典型地個別地為每一百份含矽聚合物至多約1.0份，或總共為每100份含矽聚合物至多約1.5份。Preferred additives for use in the thermoset silicon-containing polymer compositions herein are curing agents, such as peroxide curing agents, which are typically incorporated at about 0.5 to about 5.5 parts per 100 parts of polysiloxane polymer, or In other systems it is a platinum catalyst in an amount from about 0.0005 to about 0.0015 parts per 100 parts of silicon-containing polymer. Other preferred additives include colorants and pigments such as white (titanium oxide), yellow (iron oxide or azoiron), blue (phthalocyanine GS or ultramarine) and/or green (phthalocyanine) BS), the amounts may vary, but are typically up to about 1.0 parts per 100 parts of silicon-containing polymer individually, or up to about 1.5 parts in total per 100 parts of silicon-containing polymer.
除任何特定固化系統外，諸如流變或搖變劑之該等添加劑視情況存在，且可以至多約50重量%之總量的量併入。In addition to any particular curing system, such additives such as rheological or thixotropic agents are optionally present and may be incorporated in amounts up to about 50% by weight of the total amount.
視所用固化系統而定，可針對系統調整相關固化劑之程度。因為該等固化系統為此項技術中已知的，所以本文中可使用與如上文所提及相同的系統。本發明內使用之熱固性聚矽氧烷之較佳實例包括市售聚矽氧烷，例如但不限於具有鉑固化系統之雙組分聚矽氧烷，包括可購自Dow Chemicals之以下材料：DowSil®SE 1700、Xiameter™ RBL 2004-50、Silastic™ 9200-50、Silastic™ 3D LC-3335及Silastic™ 7-5860；來自DuPont之Liveo™ C6-770；及來自Elkem之AMSil™ 20501-50及AMSil™ 20501-70，以及具有過氧化物固化系統之單組分聚矽氧烷，諸如可購自Primetech® Silicones之AMS聚矽氧烷3302H型。該等系統可按其製造商建議進行使用及組合。在本文中亦可使用符合類似準則及能力之其他聚矽氧烷。不意欲限制本發明之範圍，本文中使用之較佳聚矽氧烷例如在約10 mm/s至約100 mm/s之目標擠壓速度下操作，以便在零剪切速率下具有高黏度，例如在零剪切速率下具有約20,000泊至約100,000泊之黏度的彼等及/或在高剪切速率下具有低黏度之彼等，例如在約100/s至約1,000/s下具有約2,000泊至約18,000泊之黏度的彼等，其中高剪切速率意謂約100/s至約1000/s之聚矽氧烷剪切速率。該等材料亦較佳，其可展現如本文提及之賓漢塑膠行為。Depending on the curing system used, the level of relevant curing agents can be adjusted to the system. Since such curing systems are known in the art, the same systems as mentioned above may be used herein. Preferred examples of thermoset polysiloxanes for use within the present invention include commercially available polysiloxanes such as, but not limited to, two-component polysiloxanes with platinum cure systems, including the following materials available from Dow Chemicals: DowSil ®SE 1700, Xiameter™ RBL 2004-50, Silastic™ 9200-50, Silastic™ 3D LC-3335 and Silastic™ 7-5860; Liveo™ C6-770 from DuPont; and AMSil™ 20501-50 and AMSil from Elkem ™ 20501-70, and one-component silicones with peroxide cure systems, such as AMS silicone type 3302H available from Primetech® Silicones. These systems may be used and combined as recommended by their manufacturers. Other polysiloxanes meeting similar criteria and capabilities may also be used herein. Without intending to limit the scope of the invention, preferred polysiloxanes for use herein operate, for example, at a target extrusion speed of about 10 mm/s to about 100 mm/s to have high viscosity at zero shear rate, For example, those having a viscosity of about 20,000 poise to about 100,000 poise at zero shear rate and/or those having a low viscosity at high shear rate, such as having a viscosity of about 100/s to about 1,000/s. Those with a viscosity of 2,000 poise to about 18,000 poise, where high shear rate means a polysiloxane shear rate of about 100/s to about 1000/s. These materials are also preferred and can exhibit the behavior of Bingham plastics as mentioned in this article.
本文中之熱塑性組成物包括本文在一或多個強化層中所用之至少一種熱塑性材料，可為能夠經由增材製造列印之任何適合的熱塑性材料，包括但不限於聚烯烴，包括聚伸烷，諸如聚丙烯、聚乙烯、聚丁烯及聚對苯二甲酸乙二酯、聚醯胺、聚酯、聚醯亞胺、聚伸芳基醚、聚苯乙烯、聚苯乙烯-丁二烯、聚丙烯腈、聚丙烯腈-丁二烯-苯乙烯、聚苯乙烯-丙烯腈、聚苯硫醚、聚伸苯醚、與聚苯乙烯共混之聚伸苯醚、聚氧化烯及聚伸烷基醚、聚甲醛、聚酯多元醇或聚伸烷基多元醇（諸如二醇類改質聚對苯二甲酸乙二酯）、聚丙烯酸酯、聚烷基丙烯酸酯、聚乙酸乙烯酯、聚氯乙烯、聚偏二氯乙烯、聚乙酸乙烯酯、聚乙烯醇、聚縮醛、聚乙烯醚、聚偏二氟乙烯、熔融可處理的氟聚合物（包括FEP、PFA、ETFE）及聚伸芳基醚、聚伸芳基醚酮、聚伸芳基醚碸及如同在申請中的美國專利申請案第16/568,125號中所述之其他芳族聚合物、熱塑性彈性體（thermoplastic elastomer；TPE）及熱塑性聚胺甲酸酯（thermoplastic polyurethane；TPU）。適合之商業熱塑性聚胺甲酸酯包括Ninjaflex® TPU、Cheetah® TPU及Armadillo® TPU，其各自可購自NinjaTek®。適合之熱塑性彈性體（TPE）包括可購自Taulman3D.com之Taulman®塑化共聚醯亞胺TPE（plasticized copolyimide TPE；PCTPE）以及以商標名Pebax®可購自Arkema或3DXtech.com之聚醚嵌段醯胺（polyether block amide；PEBA）及可購自Evonik Industries之Vestamid® E。氟化TPE亦可使用，且可購自Solvay及Daikin Industries。此外，如上文所提及本文在強化層內使用之熱塑性材料可包括此等不同熱塑性材料之共聚物（經由隨機、嵌段或接枝聚合製得）、摻合物、共混物及複合或交聯結構，其限制條件為其各自能夠經由增材製造設備進行處理，且較佳地，其亦能夠為包含如上所述之熱固性含矽聚合物之組成物層提供強化體。Thermoplastic compositions herein include at least one thermoplastic material used herein in one or more reinforcement layers, which can be any suitable thermoplastic material capable of printing via additive manufacturing, including but not limited to polyolefins, including polyalkylenes. , such as polypropylene, polyethylene, polybutylene and polyethylene terephthalate, polyamide, polyester, polyimide, polyarylene ether, polystyrene, polystyrene-butadiene , polyacrylonitrile, polyacrylonitrile-butadiene-styrene, polystyrene-acrylonitrile, polyphenylene sulfide, polyphenylene ether, polyphenylene ether blended with polystyrene, polyoxyalkylene and poly(phenylene oxide). Alkylene ether, polyoxymethylene, polyester polyol or polyalkylene polyol (such as glycol-modified polyethylene terephthalate), polyacrylate, polyalkyl acrylate, polyvinyl acetate , polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyacetal, polyvinyl ether, polyvinylidene fluoride, melt-processable fluoropolymers (including FEP, PFA, ETFE) and Polyarylene ether, polyarylene ether ketone, polyarylene ether ketone, and other aromatic polymers, thermoplastic elastomers as described in pending U.S. Patent Application No. 16/568,125 ; TPE) and thermoplastic polyurethane (TPU). Suitable commercial thermoplastic polyurethanes include Ninjaflex® TPU, Cheetah® TPU and Armadillo® TPU, each of which is available from NinjaTek®. Suitable thermoplastic elastomers (TPEs) include Taulman® plasticized copolyimide TPE (PCTPE) available from Taulman3D.com and polyether inserts available under the trade name Pebax® from Arkema or 3DXtech.com Polyether block amide (PEBA) and Vestamid® E available from Evonik Industries. Fluorinated TPE can also be used and is available from Solvay and Daikin Industries. Additionally, as mentioned above, the thermoplastic materials used herein within the reinforcement layer may include copolymers (made via random, block or graft polymerization), blends, blends and composites or composites of these different thermoplastic materials. The cross-linked structure has the constraint that each can be processed by additive manufacturing equipment, and preferably, it can also provide reinforcement for the composition layer including the thermosetting silicon-containing polymer as described above.
該等熱塑性組成物可包括如此項技術中已知或待開發用於熱塑性組成物的一或多種添加劑及/或改質劑，其可併入至用於列印之組成物中，包括澄清劑、處理助劑、穩定劑、著色劑（諸如顏料及染料）、填料（諸如碳黑、二氧化矽、石英、熱解二氧化矽、奈米二氧化矽顆粒、玻璃纖維）及視情況存在之偶合劑、醯胺纖維、碳纖維、鬚晶、碳奈米管、UV吸收劑、UV穩定劑、潤滑劑（諸如蠟、脂肪酸）及其他流變添加劑、阻燃劑、多元醇、醯胺、呈微細粉形式之氟聚合物、氟化或全氟化聚合物添加劑、防黏連助劑（諸如二氧化矽及滑石）、光增白劑、拉伸調節劑、表面改質劑、助滑劑、分散劑、濕潤劑、助黏劑、抗靜電劑、抗微生物劑、除濕劑及已知或待開發之其他適合的熱塑性添加劑，其限制條件為該等添加劑及/或改質劑不阻止、防止或實質上阻礙藉由增材製造列印熱塑性組成物的能力。該等添加劑視情況存在，且可視組成物希望的最終特性而定以不同量併入，其限制條件為組成物仍可在增材列印機設備中列印。The thermoplastic compositions may include one or more additives and/or modifiers as known in the art or to be developed for thermoplastic compositions, which may be incorporated into compositions for printing, including fining agents , processing aids, stabilizers, colorants (such as pigments and dyes), fillers (such as carbon black, silica, quartz, pyrolytic silica, nano-silica particles, glass fibers) and where appropriate, Coupling agents, amide fibers, carbon fibers, whiskers, carbon nanotubes, UV absorbers, UV stabilizers, lubricants (such as waxes, fatty acids) and other rheological additives, flame retardants, polyols, amide, etc. Fluoropolymers in the form of fine powders, fluorinated or perfluorinated polymer additives, anti-adhesion additives (such as silica and talc), optical brighteners, stretch regulators, surface modifiers, slip agents , dispersants, wetting agents, adhesion promoters, antistatic agents, antimicrobial agents, dehumidifiers and other suitable thermoplastic additives known or to be developed, with the restriction that these additives and/or modifiers do not prevent, Prevent or substantially hinder the ability to print thermoplastic compositions via additive manufacturing. Such additives are optionally present and may be incorporated in varying amounts depending on the desired final properties of the composition, with the proviso that the composition can still be printed in an additive printer device.
在本文中之方法的一個具體實例中，提供包括第一熱固性含矽聚合物之第一組成物，且提供可如上文所描述之熱塑性組成物。本文中列印第一熱固性含矽聚合物之至少部分層，且在本文中之一個具體實例中，亦列印熱塑性組成物之至少部分層。該等層各自較佳地使用增材製造裝置列印。如本文所用，術語「層（layer）」或「至少部分層（at least partial layer）」包括增材製造設備中之電腦設計模型中的設計層之第一厚度之完整或部分沈積（因為厚度可由擠壓機噴嘴尖端或噴嘴頭設定），且可為在該特定層中橫跨物件之整個設計寬度的固體（完整）層，或僅部分層。部分層為不橫跨物件之整個設計寬度的層，且可為例如：圖案化層，其具有跨越物件之設計寬度之全部或一部分的設計、圖案或不連續部分（該圖案化層可包括或可不包括超過一種材料）；兩種不同材料之部分層，其以如上文所提及之圖案化列印配置於單層內，或經配置以使得部分材料層在整個設計長度或其僅一部分內處於彼此相對的相鄰並列位置。In one specific example of the methods herein, a first composition is provided that includes a first thermoset silicon-containing polymer, and a thermoplastic composition is provided that may be as described above. At least a portion of the layer of the first thermoset silicon-containing polymer is printed herein, and in one embodiment herein, at least a portion of the layer of the thermoplastic composition is also printed. Each of these layers is preferably printed using an additive manufacturing device. As used herein, the term "layer" or "at least partial layer" includes the complete or partial deposition of a first thickness of a designed layer in a computer design model in an additive manufacturing device (as the thickness can be determined by extruder nozzle tip or nozzle tip setting) and can be a solid (complete) layer spanning the entire design width of the object in that particular layer, or only a partial layer. A partial layer is a layer that does not span the entire design width of the object, and may be, for example, a patterned layer having a design, pattern, or discontinuity that spans all or a portion of the design width of the object (the patterned layer may include or may not include more than one material); partial layers of two different materials arranged within a single layer with patterned printing as mentioned above, or configured so that partial layers of material are present over the entire design length or only a portion thereof Located adjacent to each other.
作為一實例，設計圖案，例如網格設計圖案或其他設計圖案或不連續層中之部分層可作為強化層併入複合層或實質上完整層內，可在複合物件內形成為強化或其他層。此允許具有強化體點之層位於在其他固體列印層中及/或纏結作為分別列印之層獨立地列印的多種聚合物，但該纏結在相同水平之z方向深度下在物件中發生（例如熱塑性聚合物之網格設計圖案層及熱固性含矽聚合物之填充層，該填充層可填充網格中之開口及/或亦可用熱固性含矽聚合物之實質上完整層覆蓋該等開口）。As an example, a design pattern, such as a grid design pattern or other design pattern, or portions of a discontinuous layer may be incorporated into a composite layer or a substantially complete layer as a reinforcement layer, and may be formed as reinforcement or other layers within the composite article. . This allows layers with reinforced body points to be located within other solid printed layers and/or to tangle multiple polymers printed independently as separately printed layers, but the tangle is at the same horizontal z-depth within the object occurs (for example, a grid design pattern layer of a thermoplastic polymer and a filling layer of a thermosetting silicon-containing polymer, which can fill the openings in the grid and/or can also be covered with a substantially complete layer of the thermosetting silicon-containing polymer. Wait for the opening).
作為另一實例，若列印具有圓截面之強化物件，亦即具有自其延伸穿過之開口的固體圓柱或管狀物件，則各列印層可包括超過一種不同寬度之材料以形成環形形狀。在管狀物件之情況下，界定開口之層中正在列印的一或多個間隙應在作為部分層的列印層左側，一旦層高度達到界定開口之高度，則層應包括一或多種材料，諸如在層外部部分上以及在該層之寬度的內部部分上在物件之寬度內列印有第一熱固性含矽聚合物的部分層，可將列印有包括熱塑性材料之強化組成物之部分層列印，該部分層與外部部分列印層相鄰，保留中心間隙以界定該開口之列印。因此，具有開口之兩個層複合物可藉由使用完整層及部分層或留下間隙以適應設計來列印。As another example, if printing a reinforced object with a circular cross-section, that is, a solid cylindrical or tubular object with an opening extending therethrough, each printed layer may include more than one material of different widths to form a ring shape. In the case of tubular objects, the gap or gaps being printed in the layer defining the opening shall be to the left of the printed layer as part of the layer. Once the layer height reaches the height defining the opening, the layer shall include one or more materials, A partial layer may be printed with a reinforced composition including a thermoplastic material, such as a partial layer of a first thermoset silicon-containing polymer printed on an outer portion of the layer and an inner portion of the width of the layer within the width of the article. For printing, this partial layer is adjacent to the outer partial printing layer, leaving a central gap to define the opening for printing. Therefore, a two-layer composite with openings can be printed by using full and partial layers or leaving gaps to suit the design.
如本文所用，當一般提及術語「層」時，所屬技術領域中具有通常知識者因此將基於本揭示內容意圖理解，且本文中之申請人意欲使用術語「層」包括完全完整層、部分層或圖案化及部分層，且除非該層另外明確描述為特定類型之層，否則可在給定層（亦即在電腦設計模型內具有給定設計寬度及長度的設計層之第一厚度）內包括一或多種材料。術語「至少部分層」意欲與「層」互換使用，但意欲闡明層之某一部分包括正在列印之材料，且該材料可視設計而定在層之一些、大部分或全部內列印。As used herein, when referring generally to the term "layer," one of ordinary skill in the art will therefore understand that based on this disclosure, and applicants herein intend that the term "layer" includes fully complete layers, partial layers or patterned and partial layers, and may be within a given layer (i.e., the first thickness of a design layer with a given design width and length within the computer design model) unless the layer is otherwise expressly described as a specific type of layer Includes one or more materials. The term "at least part of a layer" is intended to be used interchangeably with "layer," but is intended to clarify that a portion of a layer includes the material being printed, and that the material may be printed within some, most, or all of the layer, depending on the design.
因此，本發明中之包括第一熱固性含矽聚合物之第一組成物及熱塑性組成物在本文中之一個具體實例中經列印以便各自形成作為至少部分層的層，以使得其可如上文所提及連續或在同一層內經列印。在一個具體實例中，首先列印包括第一熱固性含矽聚合物之第一組成物，且可將其列印在基板上。包括熱塑性組成物之強化層可為至少部分層或完整層，可將其列印在包括第一熱固性含矽聚合物之第一組成物之層上，或若該強化層各者僅為部分層，則可將其列印在同一層中。該等層可如上文所提及進行列印，或可顛倒，以使得將熱塑性組成物列印為第一至少部分層，且將熱固性含矽聚合物組成物列印在熱塑性組成物層上，以熱塑性組成物形式或列印在同一層內（作為部分層）。然而，因為熱塑性組成物意欲在本文中之複合物中主要作為強化體層，所以在本文中之較佳具體實例中，較佳地，熱固性含矽聚合物組成物列印在第一層中，且強化劑列印在第一層上。Therefore, the first composition including the first thermosetting silicon-containing polymer and the thermoplastic composition of the present invention are in one embodiment herein printed so as to each form a layer as at least a partial layer such that it can be as above References are printed consecutively or within the same layer. In a specific example, a first composition including a first thermosetting silicon-containing polymer is first printed and may be printed on the substrate. The reinforcement layer including the thermoplastic composition may be at least a partial layer or a complete layer, which may be printed on a layer of the first composition including the first thermosetting silicon-containing polymer, or if the reinforcement layers are each only a partial layer , they can be printed on the same layer. The layers may be printed as mentioned above, or may be reversed such that the thermoplastic composition is printed as the first at least partial layer, and the thermosetting silicon-containing polymer composition is printed on the thermoplastic composition layer, In the form of a thermoplastic composition or printed within the same layer (as a partial layer). However, since the thermoplastic composition is intended primarily as a reinforcement layer in the composites herein, in the preferred embodiments herein, preferably the thermoset silicon-containing polymer composition is printed in the first layer, and Enhancers are printed on the first layer.
在一個具體實例中，在列印熱塑性組成物之一或多個強化層之前，熱固性含矽聚合物組成物之多個層（完整或部分）可列印在第一層上或列印為第一層（其中第一層在此情況下可包括多個層）。在本文中之另一具體實例中，亦有可能將熱固性含矽聚合物組成物層、熱塑性組成物之強化層、及隨後熱塑性組成物之一或多個額外層列印在強化層頂部上。因此，在本文中之不同具體實例中，包括熱固性含矽聚合物之組成物層及包括熱塑性組成物之強化層可如所提及分層、顛倒分層、連續且以交替方式分層或以其內各自包括單一組成物之連續層的交替層形式分層。該等分層列印結構中之各者形成複合列印物件，其具有熱固性含矽聚合物組成物之至少一個列印層及包括熱塑性組成物之至少一個強化層。該等結構內之各該層亦可包括如上文所提及之部分層及列印在同一層內之其他材料。In one specific example, multiple layers (complete or partial) of the thermoset silicon-containing polymer composition can be printed on a first layer or as a third layer prior to printing one or more reinforcing layers of the thermoplastic composition. One layer (where the first layer in this case may include multiple layers). In another embodiment herein, it is also possible to print a layer of thermoset silicon-containing polymer composition, a reinforced layer of thermoplastic composition, and then one or more additional layers of thermoplastic composition on top of the reinforced layer. Thus, in various embodiments herein, the composition layer including the thermoset silicon-containing polymer and the reinforcement layer including the thermoplastic composition may be layered as mentioned, layered upside down, layered continuously and in an alternating manner, or in The layers are layered in the form of alternating layers each including successive layers of a single composition. Each of the layered printing structures forms a composite printed object having at least one printing layer of a thermosetting silicon-containing polymer composition and at least one reinforcement layer including a thermoplastic composition. Each layer within these structures may also include partial layers as mentioned above and other materials printed within the same layer.
所得複合物件可在逐層製程中進行增材製造以形成複合物件之後按原樣使用。該等三維列印複合物件可按原樣用作作為直接地壓縮模製之物件的替代方案形成的新穎部分，或可藉由退火、烘箱處理、壓縮模製或用於強化或用於其他處理之複合技術中之塑膠物件已知的其他形成製程經進一步熱處理。The resulting composite object can be used as is after being additively manufactured in a layer-by-layer process to form the composite object. These three-dimensional printed composite objects may be used as-is as novel parts formed as an alternative to directly compression-molded objects, or may be annealed, oven-processed, compression-molded, or used for strengthening or other processing. Other processes known for forming plastic objects in composite technology are further heat treated.
另外，藉由增材製造形成之三維列印複合物件可進一步用作饋料或形成材料，例如其可經列印為方塊、球形式或其類似形式及/或進一步粒化或研磨為較小物件，且該等饋料或形成材料可為經由其他熱模製技術形成另一成形物件的基礎，以便形成桿、環或其他三維物體。使用三維列印物件或由其形成之物件可使用已知或待開發之再循環技術（諸如引入長絲）進一步再循環，以進一步用於後續增材製造方法中或用於熱模製製程中。In addition, the three-dimensional printed composite object formed by additive manufacturing can be further used as a feed or forming material. For example, it can be printed into squares, spheres or similar forms and/or further granulated or ground into smaller sizes. object, and such feeds or forming materials may be the basis for forming another formed object via other thermal molding techniques to form rods, rings, or other three-dimensional objects. Objects using or formed from 3D printed objects can be further recycled using known or yet to be developed recycling techniques (such as the introduction of filaments) for further use in subsequent additive manufacturing methods or for use in thermal molding processes. .
在本文中之其他具體實例中，可將包含第二熱固性含矽聚合物之第二組成物引入本文中之複合物中。可將此類第二組成物列印在包括第一熱固性含矽聚合物之第一組成物上或列印在至少一個強化層上，且亦可將其列印在其他層中之一者內作為部分層，諸如呈相鄰或圖案化組態。視需要，強化層亦可為分開的或部分的。舉例而言，可形成至少一個第一含聚矽氧烷組成物層，可將具有第一熱塑性材料之至少一個第一強化層列印在第一含聚矽氧烷組成物層上。在彼等層之間、在其頂部上或在其內，以部分或圖案化方式，可視情況列印具有第二聚矽氧烷聚合物之第二組成物。視情況，亦可將具有第二熱塑性材料之另一強化層列印在上文提及之層中之任一者或所有者之間或之中。在一個具體實例中，根據經圖案化設計列印具有第二熱固性含矽聚合物之第二組成物的一或多個額外的至少部分層以及第一含矽組成物之至少部分層及第一熱塑性材料之至少部分層。In other embodiments herein, a second composition comprising a second thermoset silicon-containing polymer may be incorporated into the composites herein. Such second composition may be printed on the first composition including the first thermosetting silicon-containing polymer or on at least one reinforcement layer, and may also be printed on one of the other layers As part of the layers, such as in adjacent or patterned configurations. If necessary, the reinforcement layer can also be separate or partial. For example, at least one first polysiloxane-containing composition layer may be formed, and at least one first reinforcement layer having a first thermoplastic material may be printed on the first polysiloxane-containing composition layer. A second composition having a second polysiloxane polymer is optionally printed in a partial or patterned manner between, on top of, or within the layers. Optionally, another reinforcing layer with a second thermoplastic material can also be printed between or in any of the above-mentioned layers or owners. In one specific example, one or more additional at least partial layers of a second composition of a second thermoset silicon-containing polymer and at least partial layers of a first silicon-containing composition are printed according to a patterned design. At least partial layers of thermoplastic material.
在擁有具有第二熱固性含矽聚合物之第二組成物的該等具體實例中，具有第二熱固性含矽聚合物之第二組成物與含有第一熱固性含矽聚合物之第一組成物相比可具有相同或不同熱固性含矽聚合物。因此，組成物可因添加劑、使用相同熱固性含矽一級聚合物在列印層內共混或添加其他聚合物而不同，只要兩種組成物使用賓漢塑膠之特徵可流動且能夠使用增材製造設備列印即可。可替代地，兩種不同熱固性含矽聚合物可用於第一及第二熱固性含矽聚合物組成物中，除此之外，組成物中之添加劑及/或改質劑或其他聚合物（若存在）亦可為相同基礎組成物或可不同。In those embodiments having a second composition having a second thermosetting silicon-containing polymer, the second composition having the second thermosetting silicon-containing polymer is in phase with the first composition having a first thermosetting silicon-containing polymer. Ratios may have the same or different thermoset silicon-containing polymers. Therefore, compositions can differ due to additives, use of the same thermoset silicon-containing primary polymer blended within the print layer, or the addition of other polymers, as long as both compositions use the characteristics of Bingham plastics to be flowable and capable of using additive manufacturing The device can print. Alternatively, two different thermosetting silicon-containing polymers may be used in the first and second thermosetting silicon-containing polymer compositions, in addition to additives and/or modifiers or other polymers in the compositions (if exist) may be of the same basic composition or may be different.
類似地，可存在超過一種類型之熱塑性材料用於熱塑性組成物中，且在不同強化層中可存在超過一種熱塑性組成物。該等複合物可因層及組成物而不同，其限制條件為具有至少一種第一熱固性含矽聚合物之第一組成物的至少一個層及包括至少一種熱塑性組成物的至少一個強化層併入所列印複合物中，無論該等層是否在整個設計長度內完整或部分及/或無論層是否在同一設計層內包括一或多種材料。Similarly, there may be more than one type of thermoplastic material used in the thermoplastic composition, and more than one thermoplastic composition may be present in different reinforcement layers. The composites may vary by layer and composition, with the proviso that at least one layer having a first composition of at least one first thermosetting silicon-containing polymer and at least one reinforcing layer including at least one thermoplastic composition are incorporated therein. In a printed composite, whether such layers are complete or partial throughout the entire design length and/or whether or not the layers include one or more materials within the same design layer.
與先前具體實例一樣，複合物之該等其他具體實例亦可在列印後進一步處理或以列印狀態用於列印物件中。進一步處理可包括表面整理加工、拋光、退火或進一步熱模製使用增材製造設備由本文提及之複合物形成的成品列印三維物件。在此類設備中，複合物使用如增材製造技術中所已知的電腦設計模型逐層形成，在此情況下，三維物體及其圖案經預程式化至三維列印設備上安裝之現有軟體或出於此目的經設計之開放原始碼軟體中。然而，對於具有不同材料之多層的該等複合物、對於本文中形成之多層複合物，申請人已進一步開發具有多層列印之能力所用之較佳設備，以使得複合物與標準增材製造設備相比可以更快及更精確方式製得。As with the previous embodiments, these other embodiments of the composite may also be further processed after printing or used in a printed state in a printed object. Further processing may include surface finishing, polishing, annealing or further thermal molding of finished printed three-dimensional objects formed from the composites mentioned herein using additive manufacturing equipment. In such devices, the composite is formed layer by layer using computer design models as known in additive manufacturing technology. In this case, the three-dimensional objects and their patterns are pre-programmed into the existing software installed on the three-dimensional printing device. or in open source software designed for this purpose. However, for such composites with multiple layers of different materials, for the multi-layer composites formed herein, Applicants have further developed better equipment with the ability to print multiple layers so that the composites are compatible with standard additive manufacturing equipment can be produced in a faster and more precise manner than
圖1及1A展示增材製造設備100之一較佳具體實例的視圖。圖1提供設備之示意性圖示，且圖1A為安裝用於如上所述根據本發明形成三維複合物件之設備的透視圖。1 and 1A show views of a preferred embodiment of an additive manufacturing apparatus 100. Figure 1 provides a schematic illustration of the apparatus, and Figure 1A is a perspective view of the apparatus installed for forming three-dimensional composite objects in accordance with the present invention as described above.
如所示，支架整件102在整件102之任一側上具有複數個縱向框架構件104，且具有用於支撐噴嘴整件114之橫向延伸框架構件106，該噴嘴整件可沿橫向延伸框架構件106中之一或兩者滑動。框架構件106在任一端連接至可滑動構件118，其為安裝在整件之任一側上的縱向框架構件104上之可滑動支撐件。驅動馬達116與可程式化控制器120及操作噴嘴整件114之列印機驅動機構132且與增材製造列印機134操作性連通地安置於滑動構件118中之一者上（如圖所示其在左手側）。As shown, the bracket unit 102 has a plurality of longitudinal frame members 104 on either side of the unit 102, and has transversely extending frame members 106 for supporting the nozzle unit 114, which may extend along the transverse frame. One or both of the members 106 slide. The frame member 106 is connected at either end to a slidable member 118, which is a slidable support mounted on the longitudinal frame member 104 on either side of the entire piece. The drive motor 116 is disposed on one of the sliding members 118 (as shown in FIG. Show that it is on the left hand side).
提供基座支撐框架108，其可為可移動的及/或與下部支架構件138可滑動嚙合。支撐框架108包括可滑動地嚙合之平台110，其可支撐用於接納三維列印物件之基板112。平台110包括安裝支柱140以使支撐基板112之中心表面142的位置穩定。A base support frame 108 is provided, which may be moveable and/or slidably engageable with the lower support member 138 . The support frame 108 includes a slidably engaged platform 110 that supports a substrate 112 for receiving a three-dimensional printed object. The platform 110 includes mounting posts 140 to stabilize the position of the central surface 142 of the supporting base plate 112 .
總體三維列印機之配置可見於大部分增材製造設備中，且如所示，包括Lulzbot Workhorse版列印機。亦可在本發明之範圍內使用具有此等特點之其他適合之商業列印機。Overall 3D printer configurations can be found in most additive manufacturing equipment and, as shown, include the Lulzbot Workhorse version of the printer. Other suitable commercial printers having these characteristics may also be used within the scope of the invention.
本文中之申請人開發本文中之噴嘴整件以在具有適合之滑動支架（諸如圖1A中所示之滑動支架）之增材製造設備中的多種市售三維列印機上起作用。Applicants herein developed the nozzle assembly herein to function on a variety of commercially available three-dimensional printers in additive manufacturing equipment with suitable sliding brackets, such as the sliding bracket shown in Figure 1A.
噴嘴整件114包括第一噴嘴126以列印包括熱固性含矽聚合物之第一組成物。第一噴嘴126較佳為加壓噴嘴，且諸如經由管125與加壓源124連通。加壓源可延行穿過控制器120以在列印時調整壓力，且加壓可由任何可接受加壓源，諸如加壓氣體（其可為加壓空氣或惰性氣體，諸如氮氣或另一壓力源）提供。加壓源124可為壓縮缸或其他線內空氣或氣體源。較佳地，如此項技術中已知，任何該壓縮空氣或氣體源具有控制閥及減壓閥。The nozzle assembly 114 includes a
第一噴嘴126安裝於安裝臂128中，該安裝臂經組態以支撐第一噴嘴126，同時亦遠離噴嘴延伸以支撐位於靠近第一噴嘴126處，但獨立地且穩定地安裝至安裝臂128上的第二噴嘴130。列印機驅動機構132亦位於安裝臂128上，其用於將熱塑性聚合物長絲123可操作地引入第二噴嘴130中。可將熱塑性長絲123自驅動滾筒122引入，且藉助於列印機驅動機構132在受控速度下進入噴嘴中。The
可操作作為加壓噴嘴之第一噴嘴，以使得加壓源124可操作地連接至高壓擠壓機整件144，包括如本文在圖1-5及10-14中所示。高壓擠壓機整件144可包括高壓活塞148，其如圖11中所示包括用於壓縮可流動材料之延伸活塞構件149，其在第一噴嘴126之注射器針筒146內可滑動地操作。噴嘴出口150可包括用於控制用於列印之擠壓熱固性含矽聚合物之寬度的噴嘴擠壓機尖端154。擠壓機整件與熱源連通。如所示，加熱帶或加熱圈152可圍繞噴嘴126之噴嘴端156安置。加熱帶152較佳與用於控制噴嘴之噴嘴端156或熱端之溫度的控制器120操作性連通。The first nozzle is operable as a pressurized nozzle such that the
第二噴嘴130可為經配置用於經由其噴嘴開口158列印熱塑性聚合物的任何適合之增材製造噴嘴。第二噴嘴130較佳亦與用於設置適用於擠壓所選熱塑性材料之溫度及用於經由列印機驅動機構132設置長絲之驅動速度的控制器操作性連通。Second nozzle 130 may be any suitable additive manufacturing nozzle configured for printing thermoplastic polymer through its nozzle opening 158 . The second nozzle 130 is preferably also in operative communication with a controller for setting the temperature suitable for extruding the selected thermoplastic material and for setting the drive speed of the filament via the printer drive mechanism 132 .
控制器亦較佳地藉由修改增材製造裝置可用的開放原始碼或商用軟體來程式化，以具有允許一次自一個噴嘴交替、連續或其他映射不同聚合物層的電腦設計模型。The controller is also preferably programmed by modifying open source or commercial software available for additive manufacturing equipment to have a computer-designed model that allows alternating, sequential, or other mapping of different polymer layers from one nozzle at a time.
如上文所提及，第一噴嘴126可列印物件之第一至少部分層或完整層，且程式可隨後嚙合第二噴嘴130以將完整層或部分層列印在第一至少部分層上，且其他層，諸如任一材料之第三層或其他層可隨後在完整或部分層內列印以根據設計圖案形成第二噴嘴130等等。設計層之圖案、長度及寬度及/或其厚度可經程式化至電腦設計模型中以允許個別地使用噴嘴。As mentioned above, the
如圖1-14中所示之安裝臂128經組態以具有延伸的支撐部分160，其自經組態以固定加壓第一噴嘴126之支撐底座162橫向延伸。支撐底座162界定開口164，第一噴嘴之下部噴嘴部分156可穿過該開口，且在該開口下可安置加熱帶152。延伸的支撐部分經組態以足以支撐第一噴嘴130及噴嘴整件114、列印機驅動機構132。第二噴嘴130展示為加熱擠壓機，諸如商業擠壓機Lulzbot熱塑性擠壓機。亦可使用能夠列印熱塑性塑膠之其他類似商業擠壓機。第一噴嘴126可經調適作為任何適合之加壓噴嘴，且適合之該噴嘴可以Nordson高壓擠壓機購得。The mounting
安裝臂可經由緊固件延伸穿過開口166在其後部上安裝，該等緊固件可安裝至橫向構件106，從而允許噴嘴在設備100之支架整件102上來回及上下移動。亦可使用基座支撐框架以調整物件之列印。The mounting arms may be mounted on the rear thereof via fasteners extending through the openings 166 that may be mounted to the cross member 106 to allow the nozzle to move back and forth and up and down the entire frame 102 of the device 100 . You can also use a base support frame to adjust the printing of objects.
其他機械臂或支架整件可容易地經調適以可控制地安置雙安裝噴嘴126、130。另外，如所屬技術領域中具有通常知識者在本發明之範圍內基於本揭示內容理解，安裝臂128可藉由在安裝臂上延伸支撐部分160或形成第二加壓噴嘴底座，諸如支撐底座162，以背向或正向方向橫向延伸以容納可與噴嘴126或噴嘴130中之任一者相同的第三噴嘴。包括與所示之安裝臂一致的第二安裝臂之第二噴嘴整件可控制地安裝在相同橫向構件上或在獨立懸掛及可滑動地操作的支架整件之橫向臂上亦在本發明之範圍內。此類第二噴嘴整件可使得含有矽聚合物或第二熱塑性聚合物之第二組成物以相同組態列印，且視需要在相同複合物基質中列印，其限制條件為電腦設計模型經修改以適應該列印。Other robotic arms or bracket entires can be easily adapted to controllably position the dual-mounted
在本文中之又另一具體實例中，提供一種用於形成包含熱固性含矽聚合物之複合物件的方法及設備。In yet another embodiment herein, a method and apparatus are provided for forming a composite article including a thermoset silicon-containing polymer.
對於本文中之具體實例，其中使用具有第一及/或第二熱固性含矽彈性體之組成物（亦即，可固化熱固性聚矽氧烷）以列印在聚矽氧烷/長強化纖維複合物中包含連續長強化纖維之複合物中，較佳地，連續長強化纖維併入連續的以下物質中之一或多者：碳纖維、玻璃纖維、硼纖維、氧化鋁纖維、碳化矽纖維、石英纖維及各種有機或對位芳族纖維（諸如醯胺纖維（諸如Kevlar®））、聚苯并唑（polybenzoxazole；PBO）纖維、超高分子量聚乙烯纖維、聚丙烯、聚對苯二甲酸乙二酯、聚乙烯、聚醯亞胺、聚芳酯、聚醚醯亞胺及聚乙烯醇，以及合成有機纖維，諸如嫘縈及聚丙烯腈纖維，以及天然及合成纖維共混物。天然纖維亦可單獨使用，或與如上文所提及之其他有機或合成纖維，包括角蛋白、亞麻、黏液、劍麻、***及黃麻一起使用。對於拉伸強度及較佳製造複合物特性，較佳使用碳、醯胺、玻璃或熱塑性纖維，其中碳、醯胺及玻璃尤其較佳。該等纖維可提供為單一纖維、纖維絲束、編織物、共混物及混合纖維，然而，較佳地，纖維以連續纖維形式提供至製程以便經由噴嘴饋入。纖維可視情況包括上膠、塗層或處理或試劑以增強列印彈性體物件內的黏附。纖維亦可具有如本文進一步論述之共擠壓塗層。For specific examples herein, compositions having first and/or second thermoset silicon-containing elastomers (i.e., curable thermoset polysiloxanes) are used to print on polysiloxane/long reinforcing fiber composites In composites containing continuous long reinforcing fibers, preferably, the continuous long reinforcing fibers are incorporated into one or more of the following continuous substances: carbon fiber, glass fiber, boron fiber, alumina fiber, silicon carbide fiber, quartz Fibers and various organic or para-aromatic fibers (such as amide fibers (such as Kevlar®)), polybenzo Azole (polybenzoxazole; PBO) fiber, ultra-high molecular weight polyethylene fiber, polypropylene, polyethylene terephthalate, polyethylene, polyimide, polyarylate, polyetherimide and polyvinyl alcohol, and Synthetic organic fibers, such as rayon and polyacrylonitrile fibers, and natural and synthetic fiber blends. Natural fibers can also be used alone or together with other organic or synthetic fibers as mentioned above, including keratin, flax, mucilage, sisal, hemp and jute. For tensile strength and better composite manufacturing properties, carbon, amide, glass or thermoplastic fibers are preferably used, with carbon, amide and glass being particularly preferred. The fibers may be provided as single fibers, fiber tows, braids, blends and mixed fibers, however, preferably the fibers are provided to the process in continuous fiber form for feeding through nozzles. The fibers may optionally include sizing, coatings or treatments or reagents to enhance adhesion within the printed elastomeric object. The fibers may also have coextruded coatings as discussed further herein.
當連續纖維擠壓饋入至增材列印製程中時，較佳如下文所描述使用切割裝置，其設定為將連續強化纖維切割成程式化長纖維強化體長度，以向增材列印複合物提供單向或雙向長纖維強化體。如本文所用，列印複合物內之長纖維強化體可視列印製程及所列印之複合物的尺寸而極大地變化。纖維可提供為個別纖維，包括單絲，或以亦稱為絲束之束的形式提供。較佳地，纖維以纖維束之形式提供，其中長強化纖維束之直徑，其中纖維束中個別纖維具有約10微米至約50微米之直徑且束具有約200微米至2 mm之直徑。When the continuous fiber extrusion is fed into the additive printing process, it is preferred to use a cutting device as described below, which is configured to cut the continuous reinforcement fibers into programmed long fiber reinforcement lengths to feed the additive printing composite. The material provides unidirectional or bidirectional long fiber reinforcement. As used herein, long fiber reinforcement within a printed composite can vary greatly depending on the printing process and the dimensions of the composite being printed. Fibers may be provided as individual fibers, including monofilaments, or in bundles, also known as tows. Preferably, the fibers are provided in the form of fiber bundles, wherein the long reinforcement fiber bundles have diameters in which individual fibers in the fiber bundles have a diameter of about 10 microns to about 50 microns and the bundles have a diameter of about 200 microns to 2 mm.
在列印複合物中，較佳地，列印複合物內至少部分層中之長纖維強化體佔列印複合物之約5體積%或更多，較佳約10體積%至約60體積%，且可高達約99體積%。較佳地，列印矽/長纖維複合物中之長纖維為複合物之約5體積%至約30體積%，且最佳地其為複合物之約10體積%至約20體積%。In the printing composite, preferably, the long fiber reinforcement in at least some layers of the printing composite accounts for about 5% by volume or more of the printing composite, preferably about 10% by volume to about 60% by volume. , and can be as high as about 99% by volume. Preferably, the long fibers in the printed silicon/long fiber composite are about 5% to about 30% by volume of the composite, and optimally they are about 10% to about 20% by volume of the composite.
在此具體實例中，用於複合材料中之長纖維可自連續纖維輥、夾盤或其他連續纖維饋入裝置提供至如下文進一步描述之纖維擠壓機中，或提供為織物或其類似物。在一較佳具體實例中，使用由增材製造設備電子控制的壓輪來提供連續長纖維。如本文所用，當作為長強化纖維併入至複合物中時，連續纖維切割成在切割纖維之長維度中量測之特定長度，其一般大於約0.5吋（1.27 cm）且至多約10吋（25.4 cm）之長度，較佳約1吋（2.54 cm）至約6吋（15.24 cm）。在較大列印複合物中，尺寸可針對較大結構而變化，例如至多約3呎（91.44 cm）之結構，然而，結構及纖維之尺寸並不意欲限制本發明之範圍。長纖維一般為長徑比（ l/ d）大於約100之纖維。 In this particular example, the long fibers used in the composite may be supplied from a continuous fiber roll, chuck, or other continuous fiber feed device to a fiber extruder as further described below, or as a fabric or the like. . In a preferred embodiment, a press wheel controlled electronically by the additive manufacturing equipment is used to provide continuous long fibers. As used herein, when incorporated into a composite as long reinforcing fibers, continuous fibers are cut to a specific length measured in the long dimension of the cut fibers, which is generally greater than about 0.5 inches (1.27 cm) and up to about 10 inches ( 25.4 cm) in length, preferably about 1 inch (2.54 cm) to about 6 inches (15.24 cm). In larger print composites, the dimensions may vary for larger structures, such as structures up to about 3 feet (91.44 cm), however, the dimensions of the structures and fibers are not intended to limit the scope of the present invention. Long fibers are generally fibers with an aspect ratio ( l / d ) greater than about 100.
藉由在切割連續強化纖維費用時改變長度，可將多種長強化纖維鋪設於且列印至可固化的熱固性含矽聚合物中，使得由此形成之列印且隨後固化的物件產生長纖維強化複合物，其可視列印設計在複合物之縱向方向上或在複合物中橫向方向上提供不同程度的長纖維強化，且此外，長強化纖維可以不同方向鋪設於複合物中相同或不同層中，如上文所提及，該等層可為部分層或完整層。另外，熱固性含矽聚合物可在平行於或垂直於將連續纖維列印成複合物內之長強化纖維之方向的方向上列印於層中。此等方向亦可變化，且層變化為部分層或完整層以產生材料之不同設計及不同複合物特性。By varying lengths as the continuous reinforcing fibers are cut, a variety of long reinforcing fibers can be laid down and printed into the curable thermoset silicone-containing polymer, resulting in long fiber reinforcement in the resulting printed and subsequently cured article. Compounds whose visible print design provides varying degrees of long fiber reinforcement in the longitudinal direction of the composite or in the transverse direction of the composite, and in addition the long reinforcing fibers may be laid in different directions in the same or in different layers of the composite , as mentioned above, these layers may be partial layers or complete layers. Additionally, the thermoset silicon-containing polymer can be printed in the layer in a direction parallel or perpendicular to the direction in which continuous fibers are printed into long reinforcing fibers within the composite. These directions can also be varied and the layers changed into partial or complete layers to produce different designs of materials and different composite properties.
舉例而言，在該方法中，可在大體上橫向方向上列印包含第一熱固性含矽聚合物之第一組成物的至少部分層，且在第二大體上縱向方向上列印長強化纖維之至少部分層。此圖案亦可顛倒，其中包含第一熱固性含矽聚合物之第一組成物在大體上縱向方向上列印，且長強化纖維在大體上橫向方向上列印。For example, in this method, at least a partial layer of a first composition comprising a first thermosetting silicon-containing polymer can be printed in a generally transverse direction, and the long reinforcing fibers can be printed in a second generally longitudinal direction. at least partially. This pattern can also be reversed, with the first composition including the first thermoset silicon-containing polymer printing in a generally longitudinal direction and the long reinforcing fibers printing in a generally transverse direction.
在本具體實例中，用於形成複合物件之包括提供包括第一熱固性含矽聚合物之第一組成物。熱固性含矽聚合物可為本文中之可固化含矽聚合物中之任一者，包括上文鑑別為最適用於保持複合物三維形狀之聚合物，諸如在約10至約100 mm/s之目標擠壓速度下在零剪切速率下具有約20,000泊至約100,000泊之高黏度的彼等及/或在100/s至約1,000/s之高剪切速率下具有低黏度（約2,000泊至約18,000泊）的彼等。組成物可包括一或多種該等含矽聚合物，且可進一步包括如上文所提及之建議添加劑及固化劑中之任一者，包括在需要時改變黏度之試劑或任何適合之強化纖維（諸如短切纖維及鬚晶），其限制條件為該等添加劑及強化材料不實質上影響組成物在給定列印條件下的列印能力。In this embodiment, forming the composite article includes providing a first composition including a first thermoset silicon-containing polymer. The thermoset silicon-containing polymer may be any of the curable silicon-containing polymers herein, including those identified above as being most suitable for maintaining the three-dimensional shape of the composite, such as at about 10 to about 100 mm/s. They have a high viscosity of about 20,000 poise to about 100,000 poise at zero shear rate at the target extrusion speed and/or a low viscosity (about 2,000 poise) at a high shear rate of 100/s to about 1,000/s. to about 18,000 porridge) of them. The composition may include one or more of these silicon-containing polymers, and may further include any of the suggested additives and curing agents as mentioned above, including agents to change the viscosity if necessary or any suitable reinforcing fibers ( Such as chopped fibers and whiskers), the restriction is that these additives and reinforcing materials do not substantially affect the printability of the composition under given printing conditions.
上文提及之較佳含矽聚合物包括至少一種選自以下之群的聚合物：聚矽氧烷；聚烷基矽氧烷；聚二烷基矽氧烷；及其組合或共聚物。第一熱固性含矽聚合物亦可包含至少一個選自由以下組成之群的官能基：羥基、烷基、烯基、炔基、芳基、烷氧基、烯氧基、炔氧基、芳氧基、芳基烷基、芳基烷氧基、芳基烯氧基、乙烯基、羧基、羰基、鹵素、雜環及其氟化基團及全氟化基團。包含第一熱固性含矽聚合物之第一組成物亦可包含選自由以下組成之群的一或多種組分：固化劑、固化催化劑、有機過氧化物、水解交聯劑、矽氧烷添加劑、超高分子量矽氧烷添加劑、澄清劑、UV吸收劑、光增白劑、顏料、搖變劑、流變劑、相容劑、著色劑、穩定劑、阻燃劑、石英、二氧化矽、熱解二氧化矽、碳黑、氟化或全氟化聚合物添加劑及奈米二氧化矽顆粒。The preferred silicon-containing polymers mentioned above include at least one polymer selected from the group consisting of polysiloxanes; polyalkylsiloxanes; polydialkylsiloxanes; and combinations or copolymers thereof. The first thermosetting silicon-containing polymer may also include at least one functional group selected from the group consisting of: hydroxyl, alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy base, arylalkyl, arylalkoxy, arylalkenyloxy, vinyl, carboxyl, carbonyl, halogen, heterocycle and its fluorinated groups and perfluorinated groups. The first composition including the first thermosetting silicon-containing polymer may also include one or more components selected from the group consisting of: curing agent, curing catalyst, organic peroxide, hydrolytic cross-linking agent, siloxane additive, Ultra-high molecular weight siloxane additives, clarifiers, UV absorbers, optical brighteners, pigments, thixotropic agents, rheological agents, compatibilizers, colorants, stabilizers, flame retardants, quartz, silica, Pyrolytic silica, carbon black, fluorinated or perfluorinated polymer additives and nano-silica particles.
所提供之第一組成物列印於具有第一熱固性含矽聚合物之第一組成物的如上文所定義之「至少部分層」中。該組成物可列印於基板或現有複合物之另一層上。基板可為平坦的、彎曲的或預成形為特定組態。該等層可為在一或多個連續層中或在與強化纖維層之交替層中列印的至少部分或完整個別層。此外，具有含矽聚合物之第一組成物及長強化纖維可個別地列印於重疊或共同延伸之部分層中，其中第一組成物及長強化纖維兩者在根據設計層之單層內，該層本身可為部分或完整的，如上文所定義。A first composition is provided that is printed in "at least a portion of the layer" as defined above of the first composition having a first thermosetting silicon-containing polymer. The composition can be printed on a substrate or on another layer of an existing composite. The substrate can be flat, curved, or preformed into a specific configuration. The layers may be at least partially or completely individual layers printed in one or more consecutive layers or in alternating layers with reinforcing fiber layers. Additionally, the first composition with the silicon-containing polymer and the long reinforcing fibers can be individually printed in overlapping or coextensive partial layers, where both the first composition and the long reinforcing fibers are within a single layer according to the designed layer , the layer itself can be partial or complete, as defined above.
第一熱固性含矽聚合物之列印較佳如上文所提及進行且如針對以下增材列印設備之另一具體實例所描述，使用增材製造裝置之第一噴嘴進行，該第一噴嘴較佳經加熱且亦較佳適合於加壓列印含矽聚合物。The printing of the first thermosetting silicon-containing polymer is preferably performed as mentioned above and as described for another specific example of the additive printing apparatus below, using the first nozzle of the additive manufacturing device, the first nozzle Preferably heated and also preferably suitable for pressurized printing of silicone-containing polymers.
如上文所提及，該方法可包括在列印長強化纖維之至少部分層之前或之後在其第一至少部分層上列印具有第一熱固性含矽聚合物之第一組成物的一或多個額外的至少部分層，其亦可列印於額外的至少部分長強化纖維層中。有可能連續且以交替或設計之分層方式列印此等至少部分或完整層，在至少一個強化層上列印具有含矽聚合物之第一組成物的一或多個額外的至少部分層及包含熱塑性組成物之長強化纖維的一或多個額外的至少部分層。該等層將各自根據較佳設計圖案列印且程式化以經由增材列印裝置控制。As mentioned above, the method may include printing one or more components of a first composition of a first thermosetting silicon-containing polymer on a first at least partial layer of long reinforcing fibers before or after printing at least a partial layer of the long reinforcing fibers. An additional at least partial layer, which may also be printed on an additional at least partial layer of long reinforcing fibers. It is possible to print these at least partial or complete layers continuously and in an alternating or designed layered manner, printing one or more additional at least partial layers with a first composition of a silicon-containing polymer on at least one reinforcing layer and one or more additional at least partial layers comprising long reinforcing fibers of the thermoplastic composition. The layers will each be printed according to the preferred design pattern and programmed to be controlled via the additive printing device.
在提供連續長強化纖維之後，該（等）纖維較佳使用增材製造裝置之第二噴嘴列印在使用增材製造裝置之第一噴嘴列印的具有第一熱固性含矽聚合物之第一組成物的一或多個至少部分層上的至少部分層中。在此具體實例中，第二噴嘴為如下文進一步描述之纖維擠壓噴嘴。具有第一熱固性含矽聚合物之第一組成物的至少部分層及長強化纖維之至少部分層因此經由各別噴嘴列印成在同一層內、連續或交替的設計層內。After providing continuous long reinforcing fibers, the fiber(s) are preferably printed using the second nozzle of the additive manufacturing device on the first layer of the first thermosetting silicon-containing polymer printed using the first nozzle of the additive manufacturing device. In at least a partial layer on one or more at least partial layers of the composition. In this specific example, the second nozzle is a fiber extrusion nozzle as described further below. At least partial layers of the first composition with the first thermosetting silicon-containing polymer and at least partial layers of the long reinforcing fibers are thus printed via separate nozzles within the same layer, within continuous or alternating designed layers.
當列印連續長強化纖維時，較佳在纖維離開第二噴嘴時使用纖維切割裝置將其切割成長連續纖維。如本文所提及，長強化纖維之纖維長度可藉由列印至所要長度，使得在所得列印複合物內能夠具有多種強化圖案及位置。此外，使用第二噴嘴列印長強化纖維較佳地亦包括加熱第二纖維擠壓噴嘴。When printing continuous long reinforcing fibers, it is preferred to use a fiber cutting device to cut the fibers into long continuous fibers as they exit the second nozzle. As mentioned herein, the fiber length of long reinforcing fibers can be printed to a desired length, enabling a variety of reinforcing patterns and locations within the resulting printed composite. In addition, printing the long reinforcing fibers using the second nozzle preferably also includes heating the second fiber extrusion nozzle.
在一個具體實例中，列印至本文中之複合物內之長強化纖維經由第二噴嘴與第二噴嘴中長強化纖維上方包括一或多種可擠壓聚合材料的組成物同時共擠壓。因此，在此類具體實例中，第二噴嘴可為共擠壓噴嘴。此類噴嘴在此項技術中已知用於提供原位產生之塗層連續強化纖維。上面具有可擠壓聚合材料之該等共擠壓纖維可引入共擠壓第二噴嘴中以用於特定複合物，其中對於基質內之額外強化體需要經塗佈或保護之纖維，以增強層間黏附或在纖維與熱固性含矽聚合物之基質之間提供較佳相容性或強度。在此類具體實例中，可擠壓聚合材料可為多種熱塑性或熱固性材料或可為包含第二熱固性含矽聚合物之第二組成物。第二熱固性含矽聚合物可與如本文所描述之第一熱固性含矽聚合物相同或不同。可擠壓聚合材料亦可為使用上列熱塑性或熱固性聚合物中之任一者用於在先前具體實例中形成熱塑性強化層的熱塑性或熱固性聚合物組成物，其限制條件為其為用於在共擠壓擠壓機噴嘴中在纖維上方共擠壓之可共擠壓材料。In one specific example, long reinforcing fibers printed into the composites herein are simultaneously coextruded through a second nozzle with a composition including one or more extrudable polymeric materials above the long reinforcing fibers in the second nozzle. Thus, in such embodiments, the second nozzle may be a co-extrusion nozzle. Such nozzles are known in the art for providing in situ generated coatings of continuously reinforcing fibers. These coextruded fibers with extrudable polymeric material thereon can be introduced into a coextrusion second nozzle for specific composites where coated or protected fibers are needed for additional reinforcement within the matrix to reinforce between layers. Adhesion may provide better compatibility or strength between the fibers and the matrix of the thermoset silicon-containing polymer. In such embodiments, the extrudable polymeric material can be a variety of thermoplastic or thermoset materials or can be a second composition including a second thermoset silicon-containing polymer. The second thermoset silicon-containing polymer may be the same as or different from the first thermoset silicon-containing polymer as described herein. The extrudable polymeric material may also be a thermoplastic or thermoset polymer composition using any of the thermoplastic or thermoset polymers listed above for forming the thermoplastic reinforced layer in the previous embodiments, with the proviso that it is used in Co-extrusion A co-extruded material that is co-extruded above the fibers in the nozzle of a co-extrusion machine.
熱塑性可擠壓聚合材料之實例包括至少一種選自例如由以下組成之群的熱塑性材料：聚烯烴、聚甲醛、聚醯胺、聚酯、聚醯亞胺、聚伸芳基醚、聚伸芳基醚酮、聚伸芳基醚碸、與聚苯乙烯共混之聚伸苯醚、聚丙烯腈-丁二烯-苯乙烯、聚苯乙烯-丙烯腈、聚丙烯腈、聚苯乙烯、聚對苯二甲酸乙二酯、二醇類改質聚對苯二甲酸乙二酯、熱塑性彈性體及熱塑性聚胺甲酸酯以及其共聚物、共混物、摻合物及衍生物。包含可擠壓聚合材料之組成物可包含一或多種強化纖維，諸如短纖維或短切纖維、奈米管、碳奈米結構或鬚晶。熱固性聚合材料如上文所提及用於強化層。第二熱固性含矽組成物可為經提及用於第一熱固性含矽組成物中之彼等熱固性含矽聚合物中之任一者，包括組成物內添加劑、固化劑及強化纖維之相同選擇，其限制條件為所得組成物在連續饋入強化纖維上方可共擠壓，且較佳地其限制條件亦為在增材列印複合物中之至少部分層中沈積共擠壓聚合物塗佈之強化纖維時其可視需要切割。Examples of thermoplastic extrudable polymeric materials include at least one thermoplastic material selected from the group consisting of, for example, polyolefins, polyoxymethylene, polyamides, polyesters, polyimides, polyarylene ethers, polyarylene ethers, ether ketone, polyaryl ether ketone, polyphenylene ether blended with polystyrene, polyacrylonitrile-butadiene-styrene, polystyrene-acrylonitrile, polyacrylonitrile, polystyrene, poly Ethylene terephthalate, glycol-modified polyethylene terephthalate, thermoplastic elastomers and thermoplastic polyurethanes and their copolymers, blends, blends and derivatives. Compositions containing extrudable polymeric materials may include one or more reinforcing fibers, such as short or chopped fibers, nanotubes, carbon nanostructures, or whiskers. Thermoset polymeric materials are used as mentioned above for the reinforcing layer. The second thermosetting silicon-containing composition may be any of those thermosetting silicon-containing polymers mentioned for use in the first thermosetting silicon-containing composition, including the same selection of additives, curing agents, and reinforcing fibers within the composition. , with the constraint that the resulting composition can be coextruded over a continuous feed of reinforcing fibers, and preferably also with the constraint that the coextruded polymer coating is deposited in at least some of the layers in the additive printing composite When reinforcing fibers, they can be cut as needed.
在本文中之較佳具體實例中，強化纖維並非經共擠壓而是使用加熱第二噴嘴直接列印，該加熱第二噴嘴為具有加熱第二噴嘴之纖維擠壓加熱擠壓機。在任何上文所提及之類型的連續饋入且較佳短切強化纖維/含矽聚合物複合物列印具體實例中，該方法亦可包括將藉由該方法形成之所得複合物件壓縮模製成經改質複合物件。In the preferred embodiment herein, the reinforcing fibers are not co-extruded but directly printed using a heated second nozzle, which is a fiber extrusion heated extruder with a heated second nozzle. In any of the above mentioned types of continuously fed and preferably chopped reinforcing fiber/silicon-containing polymer composite printing embodiments, the method may also include compression molding the resulting composite object formed by the method. Made into modified composite objects.
所得物件可為由本文所提及之方法之此具體實例形成的三維複合物件，其具有包括具有熱固性含矽聚合物之第一組成物的至少部分層中之至少一者及長強化纖維之至少一個部分層中之至少一者的複合結構。在一個具體實例中，其亦可包括第二或更多熱固性含矽聚合物之至少部分層以及其他類型之連續饋入且切割至應有大小的本文所提及之一或多種類型的強化纖維。另外，呈層形式之該（等）連續纖維可以多種類型提供，諸如上膠纖維、未上膠纖維、乾燥纖維、預處理纖維或與如上文所提及之可擠壓聚合物材料共擠壓的纖維。The resulting article may be a three-dimensional composite article formed by this embodiment of the method mentioned herein, having at least one of the at least partial layers comprising a first composition having a thermosetting silicon-containing polymer and at least one of the long reinforcing fibers. A composite structure with at least one of its partial layers. In a specific example, it may also include at least partial layers of second or more thermosetting silicon-containing polymers and other types of reinforcing fibers of one or more types mentioned herein that are continuously fed and cut to size. . Additionally, the continuous fiber(s) in the form of layers may be provided in a variety of types, such as sized fibers, unsized fibers, dry fibers, pre-treated fibers or co-extruded with extrudable polymer materials as mentioned above. of fiber.
該（等）三維物件可為O型環、密封件、密封墊、醫療裝置、醫療植入物或該等裝置及植入物之零件或可增材列印的任何其他物品，包括如本文提及之各種其他物品。The three-dimensional object(s) may be an O-ring, a seal, a gasket, a medical device, a medical implant or parts of such devices and implants, or any other object that can be additively printed, including as provided herein. and various other items.
在此具體實例中，該方法亦可包括提供具有第二熱固性含矽聚合物之第二組成物；及使用增材製造裝置在長強化纖維之至少部分層上列印具有第二熱固性含矽聚合物之第二組成物的至少部分第一層，或根據設計圖案以交替或依序方式列印此等層中之各者。具有第二熱固性含矽聚合物之此類第二組成物可藉由經由用於引入具有第一熱固性含矽聚合物之第一組成物的相同第一噴嘴交替其引入，藉由在長強化纖維上方共擠壓具有第二熱固性含矽聚合物材料之第二組成物（使用共擠壓噴嘴作為本文中之第二纖維擠壓噴嘴）及/或藉由引入專用於引入包括第二熱固性含矽聚合物之第二組成物的第三安裝噴嘴來引入。In this specific example, the method may also include providing a second composition having a second thermoset silicon-containing polymer; and using an additive manufacturing device to print on at least a portion of the layer of long reinforcing fibers a second composition having the second thermoset silicon-containing polymer. At least part of the first layer of the second composition of the object, or each of these layers is printed in an alternating or sequential manner according to a design pattern. Such second compositions having a second thermosetting silicon-containing polymer may be introduced by alternating them through the same first nozzle used to introduce the first composition having a first thermosetting silicon-containing polymer, by adding in the long reinforcing fibers. Co-extrude a second composition having a second thermoset silicon-containing polymer material above (using a co-extrusion nozzle as the second fiber extrusion nozzle herein) and/or by introducing a second composition including a second thermoset silicon-containing polymer material The second composition of polymer is introduced through a third installed nozzle.
在此類方法具體實例中，具有第二熱固性含矽聚合物之第二組成物的第一至少部分層可為完整層或部分層，且第一熱固性含矽聚合物及第二熱固性含矽聚合物可彼此相同或不同。舉例而言，在共擠壓具體實例中，可能適用的是使用相同聚合物以使可能原本難以列印及鋪設至含矽聚合物基質中的纖維相容或引入該纖維。In such method embodiments, the first at least partial layer of the second composition having the second thermoset silicon-containing polymer can be a complete layer or a partial layer, and the first thermoset silicon-containing polymer and the second thermoset silicon-containing polymer Things can be the same or different from each other. For example, in coextrusion embodiments, it may be useful to use the same polymer to compatibilize or incorporate fibers that may otherwise be difficult to print and lay into a silicon-containing polymer matrix.
該方法可進一步包括重複步驟，根據電腦設計模型上文提及之各種步驟，以使用增材列印裝置，較佳本文提及之增材列印裝置形成三維或其他物件。The method may further include repeating the above-mentioned steps according to the computer design model to form three-dimensional or other objects using an additive printing device, preferably the additive printing device mentioned herein.
該方法亦可包括藉由交替通過第一噴嘴之饋料，或使用第三或第四額外加熱噴嘴將另一熱塑性強化層引入至本文中形成之聚矽氧烷/長強化複合物中，以產生熱固性含矽聚合物之一或多個至少部分層、熱塑性強化層之一或多個至少部分層及長強化纖維之一或多個部分層（其可視需要亦在其上併入共擠壓層）的複合物。該（等）熱塑性強化層可如上文第一具體實例中所描述。The method may also include introducing another thermoplastic reinforcement layer into the polysiloxane/long reinforcement composite formed herein by alternating feeds through the first nozzle, or using a third or fourth additional heated nozzle, to Producing one or more at least partial layers of thermosetting silicon-containing polymer, one or more at least partial layers of thermoplastic reinforcing layers, and one or more partial layers of long reinforcing fibers on which coextrusion is optionally incorporated layer) compound. The thermoplastic reinforced layer(s) may be as described above in the first specific example.
該方法亦可包括使用及遵循經設計圖案列印複合物件，其具有具第一熱固性含矽聚合物之第一組成物的一或多個額外的至少部分層及長強化纖維之一或多個額外的至少部分層，以及第二熱固性含矽聚合物之第二組成物的任何視情況選用之至少部分層，及任何視情況選用之熱塑性強化層，以及視情況使用具有在上面擠壓的可共擠壓聚合物材料之長強化纖維的至少部分層。該方法包括重複各種列印步驟以基於電腦設計模型形成物件。The method may also include using and following a designed pattern to print a composite article having one or more additional at least partial layers of a first composition of a first thermoset silicon-containing polymer and one or more long reinforcing fibers. Additional at least partial layers, and any optional at least partial layers of a second composition of a second thermosetting silicon-containing polymer, and any optional thermoplastic reinforcing layers, and optionally a layer having an extrusion layer thereon. At least partial layers of long reinforcing fibers of coextruded polymeric material. The method involves repeating various printing steps to form an object based on a computer design model.
在其中列印有長強化纖維之複合物的此具體實例中，與先前具體實例一樣，所形成之物件亦可在列印後進一步處理或以列印狀態用於列印物件中。進一步處理可包括表面整理加工、拋光、退火或進一步熱模製使用增材製造設備由本文提及之複合物形成的成品列印三維物件。In this embodiment in which a composite with long reinforcing fibers is printed, as in the previous embodiments, the object formed may also be further processed after printing or used in a printed state in a printed object. Further processing may include surface finishing, polishing, annealing or further thermal molding of finished printed three-dimensional objects formed from the composites mentioned herein using additive manufacturing equipment.
在此類設備中，複合物使用如增材製造技術中所已知的電腦設計模型逐層形成，在此情況下，三維物體及其圖案經預程式化至三維列印設備上安裝之現有軟體或出於此目的經設計之開放原始碼軟體中。然而，對於具有熱固性含矽聚合物之至少一個層及強化長纖維之層且可能具有相同或不同材料之其他層的該等複合物，已由申請人開發較佳設備之另一具體實例，其可使用且具有多層列印之能力，使得與用標準增材製造設備相比，可以更快且更精確的方式製得長纖維強化複合物。In such devices, the composite is formed layer by layer using computer design models as known in additive manufacturing technology. In this case, the three-dimensional objects and their patterns are pre-programmed into the existing software installed on the three-dimensional printing device. or in open source software designed for this purpose. However, for such composites having at least one layer of thermosetting silicon-containing polymer and a layer of reinforcing long fibers and possibly other layers of the same or different materials, another embodiment of a better apparatus has been developed by the applicant, which The availability and ability to print multiple layers allows long fiber reinforced composites to be produced faster and more accurately than with standard additive manufacturing equipment.
在此具體實例中，在列印熱固性含矽複合物中併入長強化纖維，在本文中描述且在圖31-37D及45中展示增材製造設備之另一具體實例，在本文中稱為具體實例200。在本申請案中，在具體實例100及200中，使用相似參考編號指示類似部分或組件。舉例而言，參考編號126意欲指本文所描述之增材製造裝置/設備之第一具體實例100中的第一噴嘴，且參考編號226意欲指第二具體實例200之第二增材製造裝置/設備中的第一噴嘴。雖然兩個噴嘴無需相同，但在其為類似項目之情況下，其具有類似參考編號。在元件在物質材料上與具體實例不同之情況下，提供新編號或本文中描述差異。然而，由於具體實例100及200中之各者中的許多元件可使用不同品牌或類型之組件元件（其中一些為市售的）產生，因此除非指出受限，否則如所示的組件之變化及修改在本發明之範圍及精神內。In this specific example, long reinforcing fibers are incorporated into a printed thermoset silicon-containing composite, described herein and another specific example of an additive manufacturing apparatus, referred to herein as Specific examples 200. Throughout this application, in specific examples 100 and 200, similar reference numbers are used to indicate similar parts or components. For example,
圖31及32A分別展示用於列印其中具有熱固性含矽聚合物及長強化纖維之複合物的增材製造設備200之較佳具體實例的正面正視圖及俯視正面透視圖。圖31提供安裝用於使用如上文所描述之長強化纖維形成根據本發明之具體實例之三維複合物件的該設備之示意性圖示。31 and 32A respectively show a front elevation view and a top front perspective view of a preferred embodiment of an additive manufacturing apparatus 200 for printing a composite having a thermosetting silicon-containing polymer and long reinforcing fibers therein. Figure 31 provides a schematic illustration of the apparatus installed for forming three-dimensional composite objects according to embodiments of the invention using long reinforcing fibers as described above.
如所示，支架整件202具有在整件202之任一側上的複數個縱向框架構件204及橫向延伸框架構件206，以及用於支撐及操作可沿橫向延伸框架構件206中之一或兩者滑動的噴嘴整件214的支撐驅動滑輪機構207。框架構件206在任一端連接至可滑動構件218，其為安裝在整件之任一側上的縱向框架構件204上之可滑動支撐件。驅動馬達216與可程式化控制器220及操作噴嘴整件214中之第二噴嘴230的列印機驅動機構232且與增材製造列印機234操作性連通地安置於滑動構件218中之一者上（如圖所示其在左手側）。As shown, the stand unit 202 has a plurality of longitudinal frame members 204 and laterally extending frame members 206 on either side of the unit 202, and one or both of the laterally extending frame members 206 may be used for support and operation. Or the sliding nozzle unit 214 supports the drive pulley mechanism 207. The frame member 206 is connected at either end to a slidable member 218, which is a slidable support mounted on the longitudinal frame member 204 on either side of the entire piece. The drive motor 216 is disposed in one of the sliding members 218 in conjunction with the programmable controller 220 and the printer drive mechanism 232 operating the second nozzle 230 in the nozzle assembly 214 and in operative communication with the additive manufacturing printer 234 on the left hand side (as shown in the picture).
提供基座支撐框架208，其可為可移動的及/或與下部支架構件238可滑動嚙合。支撐框架208包括可滑動地嚙合之平台210，其可支撐用於接納三維列印物件之基板212。基板可在底層基板表面上方具有上部摩擦表面、載體薄片或脫模薄片，其各自為視情況選用的，或為如圖31-37D及45中之具體實例200中所示之開放基板表面。在兩個具體實例中，此類額外表面為視情況選用的。平台210包括用於穩定基板212之位置的安裝支柱240。A base support frame 208 is provided, which may be moveable and/or slidably engageable with the lower support member 238 . The support frame 208 includes a slidably engaged platform 210 that supports a substrate 212 for receiving a three-dimensional printed object. The substrate may have an upper friction surface, a carrier sheet, or a release sheet, each optional, above the underlying substrate surface, or an open substrate surface as shown in embodiment 200 in Figures 31-37D and 45. In two specific examples, such additional surfaces were optional. Platform 210 includes mounting posts 240 for stabilizing the position of base plate 212 .
總體三維列印機之配置可見於大部分增材製造設備中，且如所示包括Lulzbot TAZ 5列印機，其具有TAZ Dual Extruder Tool Heat v1作為列印頭（可購自Aleph Objects公司，Loveland, CO）。亦可在本發明之範圍內使用具有此等特點之其他適合之商業列印機。The overall 3D printer configuration is found in most additive manufacturing equipment and as shown includes a Lulzbot TAZ 5 printer with a TAZ Dual Extruder Tool Heat v1 as the printhead (available from Aleph Objects, Loveland , CO). Other suitable commercial printers having these characteristics may also be used within the scope of the invention.
本文中之申請人開發本文中之噴嘴整件以在具有適合之滑動支架（諸如圖31及32中所示之滑動支架）之增材製造設備中的多種市售三維列印機上起作用。Applicants herein developed the nozzle assembly herein to function on a variety of commercially available three-dimensional printers in additive manufacturing equipment with suitable sliding stands, such as the sliding stands shown in Figures 31 and 32.
噴嘴整件214包括第一噴嘴226以列印包括熱固性含矽聚合物之第一組成物。第一噴嘴226較佳為加壓噴嘴，且諸如經由管225與加壓源224連通。加壓源可延行穿過控制器220以在列印時調整壓力，且加壓可由任何可接受加壓源，諸如加壓氣體（其可為加壓空氣或惰性氣體，諸如氮氣或另一壓力源）提供。加壓源224可為壓縮缸或其他線內空氣或氣體源。較佳地，如此項技術中已知，任何該壓縮空氣或氣體源具有控制閥及減壓閥。The nozzle assembly 214 includes a first nozzle 226 for printing a first composition including a thermoset silicon-containing polymer. The first nozzle 226 is preferably a pressurized nozzle and is in communication with a pressurized source 224, such as via a tube 225. The pressurization source may be routed through the controller 220 to adjust the pressure while printing, and the pressurization may be from any acceptable pressurization source, such as a pressurized gas (which may be pressurized air or an inert gas such as nitrogen or another stress source) provided. Pressurization source 224 may be a compression cylinder or other in-line air or gas source. Preferably, any such source of compressed air or gas has a control valve and a pressure reducing valve, as is known in the art.
第一噴嘴226安裝於安裝臂228中，該安裝臂以不同於第一具體實例之安裝臂128的方式組態，因為其支撐不同於第一具體實例之第二噴嘴組態。具體實例200之安裝臂228經組態以支撐第一噴嘴226（其可與第一具體實例100之第一噴嘴126相同），同時亦自第一噴嘴126向後延伸以支撐位於靠近第一噴嘴226處，但獨立地且穩定地安裝於安裝臂228上且安裝至該安裝臂的第二噴嘴230。列印機驅動機構232亦位於安裝臂228上，其用於將強化纖維233可操作地引入第二噴嘴230中。如圖37A-D中最佳展示，強化纖維233可由噴嘴入口開口支撐件235支撐，該入口開口支撐件具有安放支撐管237以在進入強化纖維233進入第二噴嘴230時對其進行支撐。在一較佳具體實例中，支撐管237可由多種較佳惰性材料製成，該等材料不黏合至或以其他方式影響通過的強化纖維233，例如聚四氟乙烯（PTFE）或其類似模製共聚物，諸如四氟乙烯與全氟烷基乙烯基醚之共聚物或四氟乙烯與六氟丙烯之共聚物，或引入很少摩擦阻力或不引入摩擦阻力且不對擠壓強化纖維之饋入速率作出反應或產生顯著影響或導致對纖維之顯著黏附或損害的其他相當材料。The first nozzle 226 is mounted in a mounting arm 228 that is configured differently than the mounting
連續強化纖維223可自包括驅動馬達之夾持馬達饋入機構232引入。然而，可使用任何適合、穩定且較佳可程式化饋入機構。Continuous reinforcing fibers 223 may be introduced from a clamp motor feed mechanism 232 including a drive motor. However, any suitable, stable and preferably programmable feed mechanism may be used.
作為加壓噴嘴的第一噴嘴226可經操作，使得加壓源224可操作地連接至高壓擠壓機整件244。此整件244之內部與具體實例100中之高壓整件144的內部相同，且因此可參考圖1-5及10-14展示。高壓擠壓機整件244可包括與圖11中所展示相同的高壓活塞148，其包括延伸活塞構件149以壓縮可流動材料，其在第一噴嘴126之注射器針筒146內可滑動地操作，且將在第一噴嘴226中以相同方式操作。如圖33和34中所示，噴嘴226之出口250可包括用於控制用於列印之擠壓熱固性含矽聚合物之寬度的噴嘴擠壓機尖端254。將含矽聚合物組成物以可流動形式或糊狀物形式饋入噴嘴中，並且在壓力下擠壓且加熱以列印聚矽氧烷組成物。The first nozzle 226, which is a pressurized nozzle, may be operated such that the pressurized source 224 is operably connected to the high pressure extruder assembly 244. The interior of this unit 244 is the same as the interior of the
擠壓機整件244與熱源連通。如所示，加熱帶或加熱圈252可圍繞噴嘴226之噴嘴端256安置。加熱帶252較佳與用於控制噴嘴之噴嘴端256或熱端之溫度的控制器220操作性連通。The extruder unit 244 is in communication with a heat source. As shown, a heating tape or coil 252 may be positioned around the nozzle end 256 of the nozzle 226 . The heating strip 252 is preferably in operative communication with a controller 220 for controlling the temperature of the nozzle end 256 or hot end of the nozzle.
第二噴嘴230可為適用於擠壓長強化纖維且經組態用於經由其噴嘴開口258列印此類纖維的任何適合之纖維擠壓噴嘴。第二噴嘴230較佳亦與控制器220操作性連通以設定用於擠壓所選強化纖維233之適合溫度且設置纖維之驅動速度，在本文中之較佳具體實例中亦與切割裝置270可操作相關地操作，且併入包括驅動馬達之列印機驅動機構232以受控方式操作連續纖維饋入第二噴嘴。The second nozzle 230 may be any suitable fiber extrusion nozzle suitable for extruding long reinforcing fibers and configured for printing such fibers through its nozzle opening 258 . The second nozzle 230 is preferably also in operative communication with the controller 220 to set the appropriate temperature for extruding the selected reinforcing fiber 233 and to set the driving speed of the fiber. In the preferred embodiment herein, the second nozzle 230 is also in operative communication with the cutting device 270. The printer drive mechanism 232, which operates in relation to the operation, and incorporates a drive motor to operate the continuous fiber feed second nozzle in a controlled manner.
控制器220亦較佳藉由修改增材製造裝置可用的開放原始碼或商用軟體來程式化，以具有允許自一個噴嘴交替、連續或其他映射不同熱固性聚合物層且自第二噴嘴強化纖維（無論隨後遞送還是同時遞送）的電腦設計模型。Controller 220 is also preferably programmed by modifying open source or commercially available software available for additive manufacturing devices to have features that allow for alternating, sequential, or other mapping of different thermoset polymer layers from one nozzle and reinforcing fibers from a second nozzle ( computer design model (whether delivered subsequently or simultaneously).
如上文所提及，第一噴嘴226可列印物件之第一至少部分層或完整層，且程式可隨後嚙合第二噴嘴230以將強化纖維之完整層或部分層列印在第一至少部分層上，且其他層，諸如任一材料之第三層或其他層可隨後根據設計圖案在完整或部分層內自第二噴嘴230列印。設計層之圖案、長度及寬度及/或其厚度可經程式化至電腦設計模型中以允許個別地使用噴嘴。As mentioned above, the first nozzle 226 can print a first at least partial layer or a full layer of the object, and the program can then engage the second nozzle 230 to print a full or partial layer of reinforcing fibers on the first at least partial layer. layer, and other layers, such as a third layer or other layers of any material, may then be printed from the second nozzle 230 in full or partial layers according to the design pattern. The pattern, length and width of the design layer and/or its thickness can be programmed into the computer design model to allow individual use of the nozzles.
如圖31-37D中所示之安裝臂228經組態以具有延伸的支撐部分260，其自經組態以固定加壓第一噴嘴226之支撐底座262縱向延伸。支撐底座262界定開口264，第一噴嘴之下部噴嘴部分256可穿過該開口，且在該開口下可安置加熱帶252。延伸的支撐部分經組態以足以支撐第一噴嘴226及噴嘴整件214以及安置於後向部分231中之第二噴嘴230，後向部分包括附接為夾持馬達之列印機驅動機構232，如所示。第二噴嘴230展示為強化纖維擠壓機，諸如可購自例如Markforged™之商業擠壓機。第二噴嘴230之下部部分239較佳亦經加熱。如所示，加熱下部部分239亦可具有加熱帶或商業熱端，諸如可使用E3D V6熱端。第二噴嘴230亦可具有用於擠壓加熱連續強化纖維之噴嘴頂端258。亦可使用能夠列印或鋪設連續強化纖維之其他類似商業連續纖維擠壓機，包括此類擠壓機，其可包括用於可擠壓聚合材料之儲集器（或能夠至外部來源接收此類材料）及用於使得可擠壓聚合材料能夠穿過連續纖維周圍的噴嘴頂端258。The mounting arm 228 as shown in Figures 31-37D is configured to have an extended support portion 260 extending longitudinally from the support base 262 configured to secure the pressurized first nozzle 226. The support base 262 defines an opening 264 through which the lower nozzle portion 256 of the first nozzle can pass and under which the heating band 252 can be positioned. The extended support portion is configured to adequately support the first nozzle 226 and the nozzle assembly 214 as well as the second nozzle 230 disposed in the rearward portion 231 that includes the printer drive mechanism 232 attached as a clamp motor. , as shown. The second nozzle 230 is shown as a reinforced fiber extruder, such as those commercially available from, for example, Markforged™. The lower portion 239 of the second nozzle 230 is preferably also heated. As shown, the heated lower portion 239 may also have a heating tape or a commercial hot end, such as an E3D V6 hot end that may be used. The second nozzle 230 may also have a nozzle tip 258 for extruding and heating the continuous reinforcing fiber. Other similar commercial continuous fiber extruders capable of printing or laying down continuous reinforcing fibers may also be used, including such extruders, which may include a reservoir for the extrudable polymeric material (or be capable of receiving this from an outside source). like material) and a nozzle tip 258 for enabling extrudable polymeric material to pass around the continuous fibers.
第一噴嘴226可調適為任何適合之加壓噴嘴，且適合之該噴嘴可以HPx Nordson高壓擠壓機自Nordson EFD, Westlake, OH購得，且使用高精度控制器，諸如亦可購自Nordson EFD之Ultimus V。然而，可以相當的能力使用能夠擠壓包括熱固性含矽聚合物之組成物的任何適合之擠壓機。The first nozzle 226 may be adapted to any suitable pressurized nozzle, and a suitable nozzle may be a HPx Nordson high pressure extruder commercially available from Nordson EFD, Westlake, OH, using a high precision controller such as also commercially available from Nordson EFD Ultimus V. However, any suitable extruder of comparable capability capable of extruding a composition including a thermoset silicon-containing polymer may be used.
安裝臂228可經由緊固件延伸穿過開口266在其一部分上安裝，該等緊固件可直接地或間接地安裝至橫向構件206，從而允許噴嘴在設備200之支架整件202上來回及上下移動。亦可使用基座支撐框架以調整物件之列印。The mounting arm 228 may be mounted on a portion thereof via fasteners extending through the opening 266 that may be mounted directly or indirectly to the cross member 206 to allow the nozzle to move back and forth and up and down the entire frame 202 of the device 200 . You can also use a base support frame to adjust the printing of objects.
其他機械臂或支架整件可容易地經調適以可控制地安置雙安裝噴嘴226、230。另外，如所屬技術領域中具有通常知識者在本發明之範圍內基於本揭示內容理解，安裝臂228可藉由在安裝臂上延伸支撐部分260或形成第二加壓噴嘴底座，諸如支撐底座262，橫向或以背向或正向方向延伸以容納可與噴嘴226或230或如具體實例100之噴嘴126或噴嘴130中之任一者具有相同組態的第三噴嘴（圖中未示）。包括與所示之安裝臂一致的第二安裝臂之第二噴嘴整件可以可控制地安裝在相同橫向構件上或在獨立懸掛及可滑動地操作的支架整件之橫向臂上亦在本發明之範圍內。此類第二噴嘴整件可使得含有視情況選用之第二矽聚合物、視情況選用之熱塑性聚合物或視情況選用之第二強化纖維的第二組成物以相同組態列印，且視需要在相同複合物基質中列印，其限制條件為電腦設計模型經修改以適應該列印。Other robotic arms or bracket entires can be easily adapted to controllably position the dual mounting nozzles 226, 230. Additionally, as one of ordinary skill in the art will understand within the scope of the present disclosure based on this disclosure, the mounting arm 228 may be formed by extending the support portion 260 on the mounting arm or forming a second pressurized nozzle base, such as the support base 262 , extending transversely or in a backward or forward direction to accommodate a third nozzle (not shown) that may have the same configuration as either nozzle 226 or 230 or
如圖33-36中所示，在本文中之較佳具體實例中，安裝臂228包括具有緊固件243之部分241，用於收納呈用於視情況選用之切割裝置247之支撐底座245形式的延伸安裝臂部分。如所示之切割裝置為經修改商業切割裝置，其具有用於操作切割裝置247之馬達249，諸如伺服馬達或類似裝置，諸如具有馬達驅動模組之NEMA 17步進馬達，視情況選用之螺線管251或用於操作安置於切割裝置247之下側上的切割機253的其他氣動裝置。裝置之切割框架具有可操作運動臂255，其由具有步進機驅動模組之馬達致動及可移動，用於在操作時定位切割裝置且可由控制器220或單獨的控制器控制。較佳地，其可由列印機之控制器，例如用於LulzBot TAZ 5列印機之RAMBo 1.3板控制。As shown in Figures 33-36, in the preferred embodiment herein, the mounting arm 228 includes a portion 241 having fasteners 243 for receiving a support base 245 for an optional cutting device 247. Extend the mounting arm section. The cutting device shown is a modified commercial cutting device having a motor 249 for operating the cutting device 247, such as a servo motor or similar device, such as a NEMA 17 stepper motor with a motor drive module, optionally a screw. Line pipe 251 or other pneumatic device for operating the cutting machine 253 located on the underside of the cutting device 247. The cutting frame of the device has an operable movement arm 255 that is actuated and movable by a motor with a stepper drive module for positioning the cutting device during operation and can be controlled by the controller 220 or a separate controller. Preferably, it can be controlled by the printer's controller, such as the RAMBo 1.3 board for the LulzBot TAZ 5 printer.
螺線管251或類似氣動或機械裝置可類似地由步進馬達之控制器或替代控制器驅動，以操作切割機253之打開及關閉操作，使得切割步驟在強化纖維離開纖維擠壓機噴嘴230時移動就位，且隨後將纖維列印或鋪設於列印熱固性含矽聚合物層上。此控制配置之圖形電路表示展示於圖45中。A solenoid 251 or similar pneumatic or mechanical device may similarly be driven by a stepper motor controller or alternative controller to operate the opening and closing operations of the cutter 253 such that the cutting step occurs before the reinforcing fiber exits the fiber extruder nozzle 230 The fibers are then moved into position and the fibers are then printed or laid on the printed thermosetting silicon-containing polymer layer. A graphical circuit representation of this control configuration is shown in Figure 45.
切割裝置亦可包括各種彈簧加壓支撐框架臂257以用於相抵於安裝臂228之後部而將裝置支撐及安置於可操作位置中，如圖33-35中最佳地展示。如圖36中所示，該等框架臂可具有稍微不同的組態，諸如使用具有替代彈簧鎖定機構259'之ABS夾架257'以將框架安裝於纖維擠壓機上。如圖36中所示，螺線管251可具有限制器261'。圖36中之切割裝置247的具體實例亦包括視情況選用之臂夾263'及拐角間隔件265'。應理解，多種切割裝置可用於在強化纖維233自第二噴嘴230擠壓時切割該強化纖維。商業切割裝置可使用或經修改以可控制且安裝至安裝臂之後部或以串聯方式或其他配置安裝，其限制條件為切割機253經安置以由列印軟體控制的給定尺寸及馬達速率可控地切割纖維，以與第一噴嘴226及第二噴嘴230相關地工作。實例包括但不限於（i）具有聽馬達、同步傳動帶傳動裝置及安裝切割刀片之旋轉切割刀片裝置；（ii）旋轉切割滾筒機構；（iii）雙輥頭切割機構；（iv）延伸的活塞操作切割刀片及其類似物。可使用任何此類切割裝置，但其必須以可控制操作方式牢固地安裝及安置以與增材製造裝置中程式化之噴嘴操作相關。The cutting device may also include various spring-loaded support frame arms 257 for supporting and positioning the device in an operative position against the rear portion of the mounting arm 228, as best shown in Figures 33-35. As shown in Figure 36, the frame arms can have a slightly different configuration, such as using an ABS clamp 257' with an alternative spring locking mechanism 259' to mount the frame on the fiber extruder. As shown in Figure 36, solenoid 251 may have a limiter 261'. The specific example of the cutting device 247 in Figure 36 also includes optional arm clamps 263' and corner spacers 265'. It should be understood that a variety of cutting devices may be used to cut the reinforcing fibers 233 as they are extruded from the second nozzle 230 . Commercial cutting devices may be used or modified to be controllable and mounted to the rear of the mounting arm or in a tandem or other configuration, with the proviso that the cutter 253 is positioned to be controllable and mounted to the rear of the mounting arm for a given size and motor speed controlled by the printing software. The fiber is cut in a controlled manner to operate in relation to the first nozzle 226 and the second nozzle 230 . Examples include, but are not limited to (i) a rotating cutting blade device with a hearing motor, a synchronized belt drive and a mounting cutting blade; (ii) a rotating cutting drum mechanism; (iii) a dual roller head cutting mechanism; (iv) an extended piston operation Cutting blades and the like. Any such cutting device may be used, but it must be securely mounted and positioned in a controlled operational manner relative to the programmed nozzle operation in the additive manufacturing device.
第一噴嘴226及第二噴嘴230中之各者較佳在電腦設計模型中經可操作地程式化以列印設計圖案中之至少部分層。若使用，則視情況選用之切割裝置類似地操作以與噴嘴226及/或230之操作串聯地工作。第一噴嘴及第二噴嘴較佳均在電腦設計模型中可操作地程式化以列印設計圖案中之第一組成物及長強化纖維的至少部分層。Each of the first nozzle 226 and the second nozzle 230 is preferably operatively programmed in the computer design model to print at least partial layers of the design pattern. If used, the optional cutting device operates similarly to work in tandem with the operation of nozzles 226 and/or 230. Preferably, both the first nozzle and the second nozzle are operatively programmed in the computer design model to print at least partial layers of the first composition and long reinforcing fibers in the design pattern.
該設備可經組態以使得第一組成物，較佳第一熱固性含矽聚合物可以長絲形式提供。第一噴嘴及第二噴嘴可為噴嘴整件之一部分，該噴嘴整件進一步包括如上文所描述的用於將第一噴嘴及第二噴嘴穩定固定在適當位置以進行串聯操作的安裝臂。安裝臂及其用於支撐第一噴嘴及第二噴嘴之支撐座較佳可操作地且可拆卸地連接至纖維切割裝置，其中支撐座可進一步具有穿過其的各別開口以支撐第一噴嘴及第二噴嘴。若使用切割裝置，如圖33-36中所示，則替代安裝臂228或除該安裝臂之外，切割裝置底座可包括用於將切割裝置底座連接至支架框架構件之安裝孔及緊固件。The apparatus may be configured such that the first composition, preferably the first thermoset silicon-containing polymer, is provided in filament form. The first and second nozzles may be part of a nozzle unit that further includes mounting arms as described above for stably fixing the first and second nozzles in position for tandem operation. The mounting arm and its support base for supporting the first nozzle and the second nozzle are preferably operably and detachably connected to the fiber cutting device, wherein the support base may further have respective openings therethrough for supporting the first nozzle and a second nozzle. If a cutting device is used, as shown in Figures 33-36, the cutting device base may include mounting holes and fasteners for connecting the cutting device base to the stand frame member instead of or in addition to the mounting arms 228.
如上文所提及之第一噴嘴226較佳為高壓活塞擠壓機，其較佳與加壓源連通且亦可使用本文提及之控制器控制。As mentioned above, the first nozzle 226 is preferably a high-pressure piston extruder, which is preferably connected to a pressurization source and can also be controlled using the controller mentioned herein.
第一噴嘴226較佳包括如上文所提及之噴嘴端部分，其具有加熱帶或經調適以圍繞噴嘴端部分256安置的其他加熱裝置，用於在具有熱固性含矽聚合物之組成物藉由噴嘴列印時加熱該組成物。第二噴嘴230較佳為如上文所描述之長強化纖維擠壓機。第二噴嘴230亦可經組態以此處之一個具體實例中接收可擠壓聚合材料，其可視情況在噴嘴內在長強化纖維上方共擠壓。The first nozzle 226 preferably includes a nozzle end portion as mentioned above with a heating tape or other heating device adapted to be positioned around the nozzle end portion 256 for use in compositions having a thermosetting silicon-containing polymer by The composition is heated when the nozzle prints. The second nozzle 230 is preferably a long reinforcing fiber extruder as described above. The second nozzle 230 may also be configured to receive an extrudable polymeric material, in one embodiment herein, which may optionally be co-extruded within the nozzle over the long reinforcing fibers.
纖維切割裝置247較佳可操作以受控間隔長度連續切割長強化纖維，該長度至少部分由所要列印速度及在列印複合物中鋪設各種層之時間決定，同時列印長強化纖維之至少部分層。第二噴嘴230可具有噴嘴端部分239及加熱帶，或如所示，經調適以圍繞噴嘴端部分安置以用於加熱長強化纖維的熱端。如圖45中所繪示的較佳具體實例中所示，纖維列印可經控制及程式化以視聚矽氧烷之列印速度及長強化纖維之纖維切割及列印鋪設以某一速率及時序切割。在第一步驟301中，使用如圖31-36中所示之較佳設備，將整個列印頭（第二噴嘴）抬升足夠距離以允許切割裝置切割機前進之空間。在步驟302中，切割裝置向下旋轉以按切割刀片位於引入連續長強化纖維之第二噴嘴230下方的方式定位。在步驟303中，啟動切割刀片且以程式化長度切割纖維。在步驟304中，切割裝置旋轉回至其在第二噴嘴列印頭後方的初始位置。在步驟305中，接著再次降低列印頭以根據程式化設計繼續列印纖維及/或聚矽氧烷。Fiber cutting device 247 is preferably operable to continuously cut long reinforcing fibers at controlled intervals, the length being determined at least in part by the desired printing speed and the time required to lay down the various layers in the print composite, while printing at least a minimum of the long reinforcing fibers. Partial layer. The second nozzle 230 may have a nozzle end portion 239 and a heating tape, or as shown, adapted to be positioned around the nozzle end portion for heating the hot ends of the long reinforcing fibers. As shown in the preferred embodiment illustrated in Figure 45, fiber printing can be controlled and programmed to occur at a certain rate in time depending on the printing speed of the polysiloxane and the fiber cutting and printing lay-up of the long reinforcing fibers. Sequential cutting. In a first step 301, using preferred equipment as shown in Figures 31-36, the entire print head (second nozzle) is raised a sufficient distance to allow room for the cutting device cutter to advance. In step 302, the cutting device is rotated downward to position the cutting blade below the second nozzle 230 where the continuous length of reinforcing fiber is introduced. In step 303, the cutting blade is activated and the fiber is cut at a programmed length. In step 304, the cutting device is rotated back to its original position behind the second nozzle print head. In step 305, the print head is then lowered again to continue printing fibers and/or polysiloxane according to the programmed design.
應進一步瞭解，饋入第二噴嘴中之長絲可在層之間變為第二熱塑性組成物，且第一噴嘴中之熱固性含矽聚合物組成物可在同一噴嘴中變為第二熱固性含矽聚合物組成物以同樣容納對相同複合結構中之超過兩種組成物進行的列印在如所示之設備之範圍內。 實施例 It will be further understood that the filaments fed into the second nozzle can be changed to a second thermoplastic composition between layers, and the thermoset silicon-containing polymer composition in the first nozzle can be changed to a second thermoset containing polymer composition in the same nozzle. Silicone polymer compositions are within the scope of the device as shown to equally accommodate printing of more than two compositions in the same composite structure. Example
實施例1：列印方法Example 1: Printing method
參看圖15，概述基礎列印方法，其經調適用於本文中之實施例中。在第一列印步驟168中，涉及在Lulzbot Cura軟體中將檔案劃分，以與Lulzbot增材製造列印機一起使用，該Lulzbot增材製造列印機經調適以具有如上文所指出之較佳特點，包括用於列印熱固性含矽聚合物組成物之第一噴嘴及列印熱塑性組成物強化層之第二噴嘴，各自安裝在如下文進一步描述之安裝臂上。劃分涉及考慮經計算之兩個噴嘴擠壓機之偏移及使用所屬技術領域中具有通常知識者已知之劃分技術輸入劃分軟體中的設置的定製設計模型。代碼針對各材料經後處理。在第二步驟170中，針對進行列印之兩種組成物中之各者的列印之各層生成G代碼（機器代碼）以形成複合物件。Referring to Figure 15, a basic printing method is outlined, adapted for use in the embodiments herein. A first printing step 168 involves partitioning the file in the Lulzbot Cura software for use with a Lulzbot additive manufacturing printer adapted to have the best performance as noted above. Features include a first nozzle for printing the thermosetting silicon-containing polymer composition and a second nozzle for printing the reinforced layer of the thermoplastic composition, each mounted on a mounting arm as further described below. Partitioning involves taking into account the calculated offset of the two nozzle extruders and entering settings into the partitioning software using partitioning techniques known to those of ordinary skill in the art. Codes are post-processed for each material. In a second step 170, G-code (machine code) is generated for each layer of the print of each of the two compositions being printed to form the composite object.
在另一步驟172中，將G代碼載入記憶卡中，且***增材製造設備中。In a further step 172, the G-code is loaded into the memory card and inserted into the additive manufacturing equipment.
使用具有鉑催化劑可固化聚矽氧烷之DowSil™ SE 1700製備用於列印之聚矽氧烷組成物。第一雙組分熱固性DowSil™ SE 1700矽如下製備。在500 ml塑膠罐中，添加136.4 g的A部分DowSil™ SE 1700（10份）及13.6 g的B部分（1份）DowSil™ SE 1700。將合併之A部分及B部分混合物充分混合直至獲得均勻的外觀以避免不完全固化。藉由充分混合之後不存在淺色條紋或大理石紋來檢查均勻性。在檢驗混合物之均勻性之後，在室溫下使用28-30吋Hg真空將其在真空烘箱中脫氣以移除氣泡。隨後，將混合物作為聚矽氧烷組成物用於如下文所述之增材列印。Polysiloxane compositions for printing were prepared using DowSil™ SE 1700 with a platinum catalyst curable polysiloxane. The first two-component thermoset, DowSil™ SE 1700 silicon, was prepared as follows. In a 500 ml plastic jar, add 136.4 g of DowSil™ SE 1700 Part A (10 parts) and 13.6 g of DowSil™ SE 1700 Part B (1 part). Mix the combined Part A and Part B mixture thoroughly until a uniform appearance is achieved to avoid incomplete cure. Check uniformity by the absence of light streaks or marbling after thorough mixing. After checking the homogeneity of the mixture, it was degassed in a vacuum oven at room temperature using 28-30 inches Hg vacuum to remove air bubbles. The mixture was then used as a polysiloxane composition for additive printing as described below.
在步驟174中，藉由安裝於根據本發明之噴嘴整件中之Nordson EFD將如上文所指出之聚矽氧烷組成物載入高壓分配工具之注射器針筒中，且將直徑為3 mm的以Lulzbot Taulman 618 Nylon出售之熱塑性聚醯胺耐綸（白色）載入安裝在噴嘴整件之安裝臂上之Lulzbot擠壓機中。當長絲吸收水時，塑膠在110℃下週期性地經歷乾燥循環。Nordson擠壓機之分配尖端為具有PTFE內襯之金屬尖端，該PTFE內層提供光滑表面且使材料容易流過噴嘴。如上所述之加熱帶附接至Nordson噴嘴擠壓機，且提供感測器以控制溫度，其較佳設定為約80℃至約100℃以用於高黏度聚矽氧烷。饋入Nordson噴嘴之活塞機構的壓力受Ultimus V精確分配器控制，該分配器與Lulzbot Workhorse 3D列印機設備上之主控制器板可操作地連通及佈線。In step 174, the polysiloxane composition as indicated above is loaded into the syringe barrel of the high pressure dispensing tool by means of the Nordson EFD installed in the nozzle assembly according to the present invention, and a 3 mm diameter Lulzbot Taulman 618 Nylon, a thermoplastic polyamide nylon sold in white, is loaded into a Lulzbot extruder mounted on a mounting arm that is integral to the nozzle. As the filaments absorb water, the plastic periodically undergoes drying cycles at 110°C. The dispensing tip of the Nordson extruder is a metal tip lined with PTFE, which provides a smooth surface and allows the material to flow easily through the nozzle. The heating tape as described above is attached to the Nordson nozzle extruder and a sensor is provided to control the temperature, which is preferably set at about 80°C to about 100°C for high viscosity polysiloxanes. The pressure of the piston mechanism feeding the Nordson nozzle is controlled by an Ultimus V precision distributor that is operatively connected and wired to the main controller board on the Lulzbot Workhorse 3D printer device.
噴嘴整件使兩個擠壓機以串聯方式移動。安裝臂經設計以將噴嘴振動的移動量降至最低，以及以確保該設備已清除增材製造列印機之所有部分，在該增材製造列印機上安裝包括安裝臂之噴嘴整件。所用安裝臂如本文中之圖式中所示。The nozzle unit allows the two extruders to move in tandem. The mounting arm is designed to minimize the amount of movement of the nozzle vibration and to ensure that the equipment has cleared all parts of the additive manufacturing printer on which the entire nozzle assembly, including the mounting arm, is mounted. The mounting arms used are as shown in the drawings in this article.
Nordson活塞擠壓機額定產生至多400 psi的擠壓力。操作增材製造裝置（Lulzbot Workhorse版列印機）以用控制器進行列印且編碼，從而允許併入兩種材料之所形成之複合樣品部分自動列印。所用列印機為Aleph Objects的熔融長絲製造（FFF）3D列印機。針對列印機之大的建構體積及整合校準系統選擇列印機。Nordson piston extruders are rated to produce up to 400 psi of extrusion force. Operate the additive manufacturing device (Lulzbot Workhorse Printer) to print and encode with the controller, allowing for automatic printing of composite sample parts formed by incorporating the two materials. The printer used is an Aleph Objects Fused Filament Fabrication (FFF) 3D printer. Choose a printer for its large build size and integrated calibration system.
列印機控制器能夠藉由改變FAN_0之狀態打開及關閉材料之壓力及流量。此允許列印機設備在無人工互動之情況下自兩個個別的噴嘴列印兩種材料。此實施方案直接地整合至劃分軟體中以使得自動進行代碼生成。Cura劃分軟體最初由Ultimaker開發，且由Aleph Objects修改以與增材製造列印機之Lulzbot線一起工作。Lulzbot Cura為本文中用於準備好製備複合部分之主要劃分軟體。The printer controller can turn the material pressure and flow rate on and off by changing the state of FAN_0. This allows the printer device to print two materials from two separate nozzles without human interaction. This implementation integrates directly into the partitioning software to enable automatic code generation. Cura demarcation software was originally developed by Ultimaker and modified by Aleph Objects to work with the Lulzbot line of additive manufacturing printers. Lulzbot Cura is the primary dividing software used in this article to prepare composite parts.
視情況存在之步驟176視情況用於熱固性聚矽氧烷，其可需要額外的熱循環（諸如後固化或退火）以使材料完全凝固。Optional step 176 is optionally provided for thermoset polysiloxanes, which may require additional thermal cycles (such as post-cure or annealing) to fully set the material.
亦使用可用過氧化物固化的熱固性AMS 3302H聚矽氧烷進行相同程序。製備聚矽氧烷，且在10 mL高壓Nordson分配注射器中，將8 g Primetech AMS 3302H載入且手動壓縮以排出大部分氣袋。隨後將注射器置放於高壓Nordson注射器推進器中。將注射器帶式加熱器緩慢加熱至聚矽氧烷擠壓所要的溫度（80-110℃），且在聚矽氧烷之溫度及流量達至穩態時開始列印。The same procedure was also performed using the peroxide-curable thermoset AMS 3302H polysiloxane. The polysiloxane was prepared and in a 10 mL high pressure Nordson dispensing syringe, 8 g of Primetech AMS 3302H was loaded and manually compressed to expel most of the air pocket. The syringe is then placed in the high pressure Nordson syringe pusher. Slowly heat the syringe belt heater to the temperature required for polysiloxane extrusion (80-110°C), and start printing when the temperature and flow rate of the polysiloxane reach a steady state.
實施例2：聚矽氧烷及熱塑性纖維複合材料Example 2: Polysiloxane and thermoplastic fiber composite material
為評估適用於形成用於本發明中之聚矽氧烷的可固化熱固性含矽聚合物，在不同溫度下基於流變特性，包括表觀剪切黏度（以Pa-s為單位）及表觀剪切速率（/s）評估若干種商業聚矽氧烷材料。初始測試用作一實例，100℉、150℉、200℉、250℉下及室溫下的PrimeTech™ AMS3302H市售聚矽氧烷提供毛細管流變儀資料，如例如圖20中所示，且亦使用動模流變儀資料進行評估。此允許鑑別適合的溫度範圍及剪切速率，從而達成列印該材料之所要黏度範圍。可針對不同的聚矽氧烷進行類似的測試以選擇用於列印之操作參數。To evaluate curable thermoset silicon-containing polymers suitable for forming polysiloxanes used in the present invention, rheological properties at various temperatures, including apparent shear viscosity in Pa-s and apparent Shear rate (/s) evaluation of several commercial polysiloxane materials. Initial testing was used as an example. PrimeTech™ AMS3302H commercially available polysiloxane at 100°F, 150°F, 200°F, 250°F, and room temperature provides capillary rheometer data, as shown, for example, in Figure 20, and also Use dynamic rheometer data for evaluation. This allows identification of the appropriate temperature range and shear rate to achieve the desired viscosity range of the material to be printed. Similar tests can be performed on different polysiloxanes to select operating parameters for printing.
使用上文在實施例1中所指出之彼等參數及製程，形成呈強化彈性管形式之樣品複合物件，包括聚矽氧烷層及聚對苯二甲酸乙二酯強化層。物件展示於圖21中。使用SEM成像分析物件，且掃描展示於圖21A中。在四個點處各自量測層厚度，且平均層厚度在下文提供於表1中。
表1
申請人為量測層間黏附開發之測試用於測試樣品材料，且測試機器以示意圖形式展示於圖22中，且機器之透視圖展示於圖22A中。在測試中，如上文所指出，以平坦層複合物形式列印四層的複合物，且將樣品在一端切割以使層1及2與層3及4分離。固定的下部底座穩定地固定層3及4，同時移動顎夾升起，且應用1 kN荷重元由機器拉起。夾具間距為3吋，且測試速率為10吋/分鐘。將試樣置放於夾具中以使得該試樣存在最小張力。測試開始，且以10吋/分鐘之速率分離夾具直至該試樣開始剝離。記錄最大負荷，且針對延伸部分繪製負荷。The test developed by the applicant to measure interlayer adhesion was used to test sample materials, and the testing machine is shown in schematic form in Figure 22, and a perspective view of the machine is shown in Figure 22A. In testing, as noted above, a four-layer composite was printed as a flat layer composite and the sample was cut at one end to separate layers 1 and 2 from layers 3 and 4. The fixed lower base holds layers 3 and 4 stably while the mobile jaw is raised and pulled up by the machine using a 1 kN load cell. The clamp spacing is 3 inches, and the test rate is 10 inches/minute. The specimen is placed in the clamps so that minimal tension exists on the specimen. The test begins and the clamps are separated at a rate of 10 inches/minute until the specimen begins to peel. The maximum load is recorded and the load is plotted for the extension.
可用於評估樣品之其他測試包括根據ASTM D412使用A型拉伸棒進行之英斯特朗牽拉測試（Instron pull test）。Other tests that can be used to evaluate samples include the Instron pull test using a Type A tensile bar according to ASTM D412.
使用耐綸6,6作為強化材料與聚矽氧烷一起形成的複雜三維列印複合物件之照片圖示包括如圖24A以照片形式展示且使用耐綸6,6及聚矽氧烷層形成的O型環及密封墊。Photographic illustrations of complex three-dimensional printed composite objects formed using nylon 6,6 as a reinforcing material together with polysiloxane include the one shown in photo form in Figure 24A and formed using nylon 6,6 and polysiloxane layers O-rings and gaskets.
實施例3：聚矽氧烷與耐綸6,6強化設計層之增材製造列印複合物Example 3: Additive manufacturing printing composite of polysiloxane and nylon 6,6 reinforced design layer
圖23A及23B展示根據設計圖案列印之不同熱塑性耐綸6,6結構上列印的聚矽氧烷層。在此特定實施例中，設計圖案提供網格設計。在圖23A中，將0-20-340網格列印為強化層，且在圖23B中，列印三角形網格。展示圍繞網格設計層具有兩個聚矽氧烷層之三層結構，且將其列印且與藉由壓縮模製聚矽氧烷層及聚對苯二甲酸乙二酯強化層形成之三層複合物進行比較。進行另一測試以比較三層結構與由相同材料形成但如上文在實施例2中所述之四層結構。結果如下在表2中所示。
表2
不同複合部分使用本文中之噴嘴整件及設備且使用聚矽氧烷聚合物及網格強化體層製備。圖16展示在聚矽氧烷層下使用耐綸網格層的Nittany Lion Penn State標誌的圖案複合物，且各自一致以形成複雜成形物件。Different composite parts were prepared using the nozzle assembly and equipment described herein and using layers of polysiloxane polymer and mesh reinforcement. Figure 16 shows a pattern composite of the Nittany Lion Penn State logo using a nylon mesh layer under a polysiloxane layer, all aligned to form a complex shaped object.
圖17展示使用具有耐綸6.6網格強化體層之聚矽氧烷層之方法中的複合物列印，其中部分聚矽氧烷層列印於網格層之頂部上。Figure 17 shows composite printing in a method using a polysiloxane layer with a nylon 6.6 mesh reinforcement layer, with part of the polysiloxane layer printed on top of the mesh layer.
圖18展示用耐綸6,6網格層列印之成品正方形複合物，所列印之網格層經由聚矽氧烷層可見。Figure 18 shows the finished square composite printed with a nylon 6,6 mesh layer visible through the polysiloxane layer.
圖19展示部分的聚矽氧烷及丙烯腈-丁二烯-苯乙烯（ABS）之介面，其中聚矽氧烷列印可看出為白色，以及ABS列印為黑色。Figure 19 shows part of the interface between polysiloxane and acrylonitrile-butadiene-styrene (ABS), where the polysiloxane print can be seen as white and the ABS print as black.
在所列印之複合物件中之各者中，聚四氟乙烯覆蓋基於鋼之焙烤薄板。不黏表面用於確保所製得的基於聚矽氧烷之複合物可在熱循環之後乾淨地移除，且鋼使得表面承受熱循環而不熔融。當提供新穎尖端時，進行校準以確定將對於所要列印速度及解析度作用最佳的設定。高壓擠壓機噴嘴之移動速度與每個時間間隔自噴嘴尖端擠出之材料的長度（亦即mm/s）直接相關。將層高度調整為小於噴嘴開口之內徑的10%，以使得該等層有機會合併在一起。此等設置可併入劃分軟體中。In each of the printed composite objects, Teflon covered a steel-based baked sheet. The non-stick surface is used to ensure that the resulting polysiloxane-based composite can be cleanly removed after thermal cycling, and the steel allows the surface to withstand thermal cycling without melting. When a novel tip is available, calibration is performed to determine the settings that will work best for the desired printing speed and resolution. The moving speed of the nozzle of a high-pressure extruder is directly related to the length of material extruded from the nozzle tip at each time interval (i.e., mm/s). Adjust the layer height to less than 10% of the inside diameter of the nozzle opening to give the layers a chance to merge together. These settings can be incorporated into the partitioning software.
實施例4：使用熱固性聚矽氧烷及熱塑性強化體之管狀結構三維增材列印Example 4: Three-dimensional additive printing of tubular structures using thermosetting polysiloxane and thermoplastic reinforcement
製備此實施例以描述聚矽氧烷（在此情況下Primetech™ AMS3302H聚矽氧烷）及熱塑性強化體，作為一實例使用熱塑性聚胺甲酸酯（TPU）在管狀結構（亦即在含有完整及部分層以界定自其穿過之開口的結構中）中之增材列印的工作流及機器製程。所用管設計根據在所請求之設計包封內多材料管形狀之發展來製得。This example was prepared to describe polysiloxane (in this case Primetech™ AMS3302H polysiloxane) and thermoplastic reinforcement, as an example using thermoplastic polyurethane (TPU) in a tubular structure (i.e. in a structure containing and partial layers to define the workflow and machine processes of additive printing in the structure from the opening it passes through. The tube design used is based on the development of a multi-material tube shape within the requested design envelope.
管形狀在多種電腦輔助設計（CAD）軟體，諸如AutoCAD®或AutoCAD® LT軟體以及Dessault Systems的SolidWorks®及Autodesk的Fusion 360®中模型化。本文中之圖25展示來自SolidWorks®之三維模型的螢幕捕獲。Tube shapes are modeled in a variety of computer-aided design (CAD) software, such as AutoCAD® or AutoCAD® LT software, as well as Dessault Systems' SolidWorks® and Autodesk's Fusion 360®. Figure 25 in this article shows a screen capture of a 3D model from SolidWorks®.
一旦在CAD軟體包中完成一系列三維模型，則將形狀導出為.STL檔案格式。該.STL檔案格式稱為表面曲面細分語言（surface tessellation language），其將三維模型之複雜數學曲率簡化為平面三角形以減少執行三維列印之工具路徑設計所需的複雜性及計算能力。對於多材料列印，已知將不同的材料形狀導出為在列印設置軟體中指定之個別的.STL檔案。Once a series of 3D models are completed in a CAD software package, the shapes are exported to .STL file format. The .STL file format is called surface tessellation language, which simplifies the complex mathematical curvature of the 3D model into planar triangles to reduce the complexity and computing power required to perform tool path design for 3D printing. For multi-material printing, it is known to export different material shapes as separate .STL files specified in the print setup software.
圖26為.STL格式檔案之網際網路（維基百科（Wikipedia））實例，展示鑑別為CM之彎曲模型與鑑別為ES之所導出.STL模型之間的差異。Figure 26 is an example of an Internet (Wikipedia) file in .STL format, showing the difference between a curved model identified as CM and an exported .STL model identified as ES.
在.STL模型準備好之後，設置列印板及參數。在此實施例中所用之軟體為Cura™ LulzBot™ 3.5.20版。Cura™（Ultimaker）為開放原始碼通用列印設置介面。所用基礎列印機（來自Aleph Objects）亦提供有Cura™之免費軟體列印設置版本。此為Cura™之LulzBot™版本。After the .STL model is ready, set the printboard and parameters. The software used in this example is Cura™ LulzBot™ version 3.5.20. Cura™ (Ultimaker) is an open source universal print configuration interface. The basic printer used (from Aleph Objects) also comes with a free software print setup version of Cura™. This is the LulzBot™ version of Cura™.
在此軟體中，.STL檔案配置於數位建構容量中，給出待列印所用之特定噴嘴，且參數經設置用於製程。參數基於待使用之形狀及材料變化。一些參數包括速度、擠壓溫度及層高度。在Cura™中，有超過100個參數可用於控制工具路徑，亦即列印機之移動及方向。圖27展示Cura™ LulzBot™ 3.6.20介面之實例。In this software, an .STL file is configured in a digital build volume, giving the specific nozzle to be printed, and the parameters are set for the process. Parameters vary based on the shape and material to be used. Some parameters include speed, extrusion temperature and layer height. In Cura™, there are over 100 parameters that can be used to control the tool path, which is the movement and direction of the printer. Figure 27 shows an example of the Cura™ LulzBot™ 3.6.20 interface.
當設置所有參數時，將STL模型「劃分」，意謂進行內部計算以將三維STL模型轉化為堆疊以表示用於列印之三維模型的一系列二維層。此等二維層解析為逐行座標機器代碼，稱為G代碼。此代碼充當引導馬達在特定時間下轉至特定角度以使噴嘴在三維空間中移動的指令。機器能夠將足夠的材料自兩個噴嘴擠出至產品中，從而使用數千次精確移動來產生三維模型的接近圖示。圖28包括數行G代碼之實例。When all parameters are set, the STL model is "partitioned," meaning that internal calculations are performed to convert the 3D STL model into a series of 2D layers that are stacked to represent the 3D model for printing. These two-dimensional layers are interpreted into line-by-line coordinate machine codes, called G-codes. This code acts as instructions for the motor to turn to a specific angle at a specific time to move the nozzle in three dimensions. The machine is able to squeeze enough material into the product from two nozzles to produce a close representation of the 3D model using thousands of precise movements. Figure 28 includes an example of several lines of G code.
三維模型、列印參數及良好調節之硬體之組合可靠地產生所要形狀。對於圖25中所示之管形狀，用在建構板上彼此內部嵌套之兩個.STL檔案列印該部分。當噴嘴以獨立的速度、溫度及形狀沈積材料時，各層可包括聚矽氧烷、熱塑性材料或此等材料之兩者之組合（包括在需要時留下間隙）。該等材料在所擠壓之材料的道路或珠粒中經分離。The combination of 3D models, printing parameters and well-tuned hardware reliably produces the desired shapes. For the tube shape shown in Figure 25, print the section using two .STL files nested within each other on the construction board. While the nozzle deposits materials at independent speeds, temperatures, and shapes, the layers can include silicone, thermoplastic materials, or a combination of both (including leaving gaps where needed). The materials are separated in paths or beads of extruded material.
當G代碼載入機器時，列印機遵循以下步驟：When the G-code is loaded into the machine, the printer follows these steps:
（1）開始讀取模型特異性G代碼檔案；(1) Start reading the model-specific G code file;
（2）加熱熱塑性塑膠列印噴嘴及視情況存在之建構板；(2) Heating the thermoplastic printing nozzle and the building plate as appropriate;
（3）移動至原位以定位起始參考點；(3) Move to the original position to locate the starting reference point;
（4）開始列印代碼：(4) Start printing code:
（a）擠壓熱塑性材料（若存在）。在此實施例中，使用熱塑性聚胺甲酸酯；(a) Extruded thermoplastic material (if present). In this example, thermoplastic polyurethane is used;
（b）將具有噴嘴之聚矽氧烷擠壓機移動至中心；(b) Move the polysiloxane extruder with the nozzle to the center;
（c）擠壓聚矽氧烷（經由自列印機至壓力調節器之信號）；(c) Extrusion of polysiloxane (via signal from printer to pressure regulator);
（d）移動直至下一層；(d) Move to the next level;
（e）擠壓聚矽氧烷；(e) Extruded polysiloxane;
（f）將用於熱塑性材料（TPU）之具有噴嘴之擠壓機移動至中心；(f) Move the extruder with a nozzle for thermoplastic materials (TPU) to the center;
（g）擠壓熱塑性材料（TPU）；(g) Extruded thermoplastic material (TPU);
（h）移動直至下一層；及(h) Move to the next level; and
（i）重複（4）（a）直至列印完成(i) Repeat (4) (a) until printing is completed
（5）返回至原位；(5) Return to original position;
（6）冷卻加熱的元件；及(6) Cooling and heating components; and
（7）結束G代碼 (7) End G code
在列印之後，多材料列印在185℃下經歷固化循環兩小時以完全固化所用特定聚矽氧烷（上文提及）且獲得所要管狀結構。After printing, the multi-material print underwent a curing cycle at 185°C for two hours to fully cure the specific polysiloxane used (mentioned above) and obtain the desired tubular structure.
圖29及30分別展示使用上述程序列印之管狀物品的俯視平面圖及透視圖，該管狀物品根據圖25中之經程式化形狀具有強化TPU之內部殼（紅色）及聚矽氧烷之外部殼（白色）。Figures 29 and 30 show respectively a top plan view and a perspective view of a tubular article printed using the above process, with an inner shell of reinforced TPU (red) and an outer shell of polysiloxane according to the stylized shape in Figure 25 (White).
實施例5：具有連續碳強化體之矽複合物結構Example 5: Silicon composite structure with continuous carbon reinforcement
在實施例中使用兩種類型的能夠固化成聚矽氧烷之熱固性含矽聚合物，亦即單組分熱固性矽及雙組分熱固性矽聚合物。Two types of thermosetting silicon-containing polymers capable of curing into polysiloxane are used in the embodiments, namely one-component thermosetting silicon and two-component thermosetting silicon polymer.
單組分熱固性含矽聚合物為Primetech™ AMS 3302H矽聚合物。在10 mL高壓Nordson™ Ultimus V分配注射器中，將8 g Primetech AMS 3302H聚矽氧烷載入且手動壓縮以排出大部分氣袋。隨後將注射器置放於包括注射器帶式加熱器之高壓Nordson HPx注射器推進器中。將注射器帶式加熱器緩慢加熱至聚矽氧烷擠壓所要的溫度（80-110℃）。The one-component thermoset silicon-containing polymer is Primetech™ AMS 3302H silicone polymer. In a 10 mL high pressure Nordson™ Ultimus V dispensing syringe, 8 g of Primetech AMS 3302H polysiloxane was loaded and manually compressed to expel most of the air pocket. The syringe was then placed in a high pressure Nordson HPx syringe advancer including a syringe band heater. Slowly heat the syringe band heater to the desired temperature for polysiloxane extrusion (80-110°C).
雙組分熱固性含矽聚合物包括以1:1之比混合的Dow® Xiameter™ RBL 2004 A部分及B部分組分。使用在不併入空氣之情況下泵送、計量且混合兩種組分的計量混合設備。若在混合期間截留氣泡，則將空氣在真空下脫氣。Two-component thermoset silicone polymer consists of Dow® Xiameter™ RBL 2004 Part A and Part B components in a 1:1 ratio. Use metered mixing equipment that pumps, meters, and mixes the two components without incorporating air. If air bubbles are trapped during mixing, degas the air under vacuum.
熱固性含矽聚合物使用雙列印頭設計整件列印，展示於圖33-35及37中。對於根據本發明之第一噴嘴中的聚矽氧烷列印，高壓活塞（Nordson™ HPx高壓分配工具，可購自Nordson EFD, Westlake, OH）與基於氣動之高精度控制器（Ultimus V，亦可購自Nordson EFD, Westlake, OH）一起使用，其中最大壓力為100 psi（7巴）。Thermosetting silicon-containing polymers are printed in a single piece using a dual print head design, as shown in Figures 33-35 and 37. For polysiloxane printing in the first nozzle according to the present invention, a high-pressure piston (Nordson™ HPx High-Pressure Dispensing Tool, available from Nordson EFD, Westlake, OH) was combined with a pneumatic-based high-precision controller (Ultimus V, also Available from Nordson EFD, Westlake, OH) with a maximum pressure of 100 psi (7 bar).
為了使用根據本發明之第二噴嘴列印連續纖維，將Markforged™纖維噴嘴安裝在E3D V6全金屬熱端（可購自E3D-Online, Oxfordshire, UK）上。Markforged™桌上型纖維擠壓機裝備有用於纖維供應之附接E3D熱端。具有筒注射器及E3D熱端之兩個噴嘴使用安裝臂安裝在LulzBot TAZ Dual Extruder Tool Head v1（Aleph Objects, Inc., Loveland, CO））中作為列印頭，如本文中圖31-35所示。由於在雙列印製程期間所需有規律地切割連續纖維，因此設計自動化材切割機，如圖33-35、37D及45中所示。將纖維列印頭及切割機安裝在LulzBot TAZ 5列印機中用於雙擠壓列印。To print continuous fibers using a second nozzle according to the present invention, a Markforged™ fiber nozzle was mounted on an E3D V6 all-metal hot end (available from E3D-Online, Oxfordshire, UK). The Markforged™ desktop fiber extruder is equipped with an attached E3D hot end for fiber supply. Two nozzles with barrel injectors and E3D hotends were mounted as printheads in the LulzBot TAZ Dual Extruder Tool Head v1 (Aleph Objects, Inc., Loveland, CO) using mounting arms, as shown in Figures 31-35 of this article . Since continuous fibers need to be cut regularly during the dual printing process, an automated material cutting machine was designed, as shown in Figures 33-35, 37D, and 45. The fiber print head and cutter are installed in the LulzBot TAZ 5 printer for dual extrusion printing.
為了獲得良好流動黏度，聚矽氧烷列印溫度需要維持在大約85-90℃，其藉由在分配器之筒注射器上附接具有與PID控制器及熱電偶（ITC-106VH, Inkbird™, Shenzhen, China）之連接的110 V 380 W加熱元件帶式加熱器（110 V 380 W，35×35 mm，Nxtop™, Shenzhen, China）來實現。此實施例中使用的兩種類型之連續纖維（碳纖維及Kevlar®纖維）的直徑為0.4 mm，其顯著小於傳統FDM型長絲之1.75 mm直徑。In order to obtain good flow viscosity, the polysiloxane printing temperature needs to be maintained at approximately 85-90°C, which is achieved by attaching a PID controller and thermocouple (ITC-106VH, Inkbird™, Shenzhen, China) connected 110 V 380 W heating element tape heater (110 V 380 W, 35 × 35 mm, Nxtop™, Shenzhen, China). The two types of continuous fibers used in this example (carbon fiber and Kevlar® fiber) have a diameter of 0.4 mm, which is significantly smaller than the 1.75 mm diameter of traditional FDM-type filaments.
如圖37中所示之PTFE管***且連接至第二纖維噴嘴以防止進入熱端供應管之纖維長絲的任何彎曲及堵塞。A PTFE tube as shown in Figure 37 is inserted and connected to the second fiber nozzle to prevent any bending and clogging of the fiber filaments entering the hot end supply tube.
應用如圖45中所示之Nema 17步進馬達及A4988步進馬達驅動器模組以控制所使用之切割裝置的切割機構旋轉及切割運動。為了在當前列印層之頂部處切割纖維，根據圖46中之步驟，列印頭設定為在切割機向下旋轉以執行切割運動之前抬升。在抬升運動期間，纖維擠壓機設定為繼續擠壓以防止擠壓機夾持及拖曳所沈積碳纖維且無意地將纖維與當前列印層分離。因此，在列印製程之設計中，使纖維擠壓與列印機之抬升及切割運動協調。The Nema 17 stepper motor and A4988 stepper motor driver module shown in Figure 45 are applied to control the rotation and cutting movement of the cutting mechanism of the cutting device used. In order to cut the fiber at the top of the current printed layer, according to the steps in Figure 46, the print head is set to be raised before the cutter is rotated downward to perform the cutting motion. During the lifting motion, the fiber extruder is set to continue extruding to prevent the extruder from clamping and dragging the deposited carbon fiber and inadvertently detaching the fiber from the currently printed layer. Therefore, the printing process is designed to coordinate fiber extrusion with the lifting and cutting motion of the printer.
為了促進列印聚矽氧烷之層與自擠出連續強化纖維切割且列印之長強化纖維之層之間的良好黏附，發現纖維擠壓噴嘴藉由經校準以與聚矽氧烷注射器尖端對準而最佳地操作。當纖維噴嘴安置得過低時，先前列印之聚矽氧烷層經歷一定損壞。當纖維噴嘴安置得過高時，強化纖維並不同樣好地黏附於聚矽氧烷層。基於在此製程中所用之材料，且歸因於此實施例中所用之連續纖維的小直徑（0.4 mm），層高度設定為0 mm以獲得強化纖維與聚矽氧烷層的良好黏附。對於各列印道路，纖維需要預擠壓較短長度。隨後，將強化纖維列印頭移動至纖維列印開始位置且在此處停止10 s，因此列印頭可預擠壓一定長度之強化纖維且確保強化纖維完全接觸聚矽氧烷層表面。在該接觸之後，強化纖維列印頭繼續向前移動以完成連續纖維之沈積。In order to promote good adhesion between the layer of printed polysiloxane and the layer of long reinforcement fibers cut and printed from the self-extruded continuous reinforcement fiber, it was found that the fiber extrusion nozzle was calibrated to match the polysiloxane syringe tip. Align and operate optimally. When the fiber nozzle is positioned too low, the previously printed polysiloxane layer experiences some damage. When the fiber nozzle is placed too high, the reinforcing fibers do not adhere to the polysiloxane layer as well. Based on the materials used in this process, and due to the small diameter of the continuous fibers used in this example (0.4 mm), the layer height was set to 0 mm to obtain good adhesion of the reinforcing fibers to the polysiloxane layer. For each printing pass, the fiber needs to be pre-extruded to a shorter length. Subsequently, the reinforced fiber print head was moved to the fiber printing start position and stopped here for 10 s, so that the print head could pre-extrude a certain length of reinforced fiber and ensure that the reinforced fiber completely contacted the surface of the polysiloxane layer. After this contact, the reinforcing fiber print head continues to move forward to complete the deposition of continuous fibers.
列印參數列於表3中。此研究中之試樣的聚矽氧烷部分用18號、1.041 mm精密分配噴嘴（Fisnar™ Micron-S）以1 mm/s列印速度及63 psi之擠壓壓力3D列印。所使用之聚矽氧烷層高度及供應壓力可在其他列印系統中針對不同噴嘴尺寸進行調整。
表3
圖38A提供如下文所描述製備之狗骨形樣品的照片。研究碳纖維強化聚矽氧烷複合物以評估纖維強化及異向性。根據ASTM D412中之標準藉由使用上文提及之設備列印來製備四種類型的狗骨形拉伸試樣。在圖38A中，展示使用以下列印之樣品：（a）垂直聚矽氧烷位向列印方向（橫向方向），但不含連續長強化纖維；（b）如（a）中之垂直位向，但包括以鋪設於列印聚矽氧烷內之層中的長強化纖維形式列印連續纖維；（c）平行位向列印聚矽氧烷（在縱向方向上），不使用連續強化纖維；及（d）如（c）中之平行位向聚矽氧烷列印，但包括使用連續纖維以在列印內之層中提供長強化纖維。Figure 38A provides a photograph of a dog bone sample prepared as described below. Carbon fiber reinforced polysiloxane composites were studied to evaluate fiber reinforcement and anisotropy. Four types of dog-bone tensile specimens were prepared according to the standards in ASTM D412 by printing using the equipment mentioned above. In Figure 38A, a sample printed using the following is shown: (a) Vertical polysiloxane position oriented in the printing direction (transverse direction), but without continuous long reinforcing fibers; (b) Vertical position as in (a) orientation, but includes printing of continuous fibers in the form of long reinforcing fibers laid in layers within the printed polysiloxane; (c) parallel orientation of printed polysiloxane (in the longitudinal direction) without the use of continuous reinforcement fibers; and (d) parallel orientation polysiloxane printing as in (c), but including the use of continuous fibers to provide long reinforcing fibers in the layers within the printing.
在圖38A中，當纖維用於四根纖維列印在兩層聚矽氧烷之間的情況時，試樣具有「夾層」結構。在約20℃之環境溫度下在配備有50 kN荷重元之MTS Criterion ®機電測試系統上以12毫米/分鐘拉伸速度進行拉伸測試。藉由在使用及不使用連續長纖維之情況下比較試樣任一列印方向來評估纖維強化效果。藉由垂直及平行位向評估異向性效應。 In Figure 38A, the sample has a "sandwich" structure when the fiber is used in the case where four fibers are printed between two layers of polysiloxane. Tensile testing was performed at an ambient temperature of approximately 20°C on an MTS Criterion ® electromechanical testing system equipped with a 50 kN load cell at a tensile speed of 12 mm/min. Fiber reinforcement was evaluated by comparing specimens in either printing direction with and without continuous long fibers. Anisotropy effects were evaluated by vertical and parallel orientations.
圖38A之狗骨形拉伸試樣藉由雙擠壓列印機用本文所描述之列印程序列印。試樣之聚矽氧烷部分藉由18號、1.041 mm精密分配噴嘴（Fisnar Micron-S, Fisnar Inc., Wayne, NJ）以1 mm/s列印速度、85℃列印溫度、1 mm層高度及63 psi之擠壓壓力列印。試樣之碳纖維部分藉由Markforged™纖維噴嘴以0.5 mm/s列印速度、270℃列印溫度及0 mm層高度列印。The dogbone tensile specimen of Figure 38A was printed by a dual extrusion printer using the printing procedure described herein. The polysiloxane part of the sample was printed using an 18-gauge, 1.041 mm precision dispensing nozzle (Fisnar Micron-S, Fisnar Inc., Wayne, NJ) at a printing speed of 1 mm/s, a printing temperature of 85°C, and a 1 mm layer. Height and extrusion pressure of 63 psi print. The carbon fiber portion of the sample was printed using a Markforged™ fiber nozzle at a printing speed of 0.5 mm/s, a printing temperature of 270°C, and a layer height of 0 mm.
圖39及40展示獲自張力測試之應變-應力曲線。在應力下，即使在拉伸張力及纖維滑移下，試樣之聚矽氧烷部分仍完全夾緊且拉伸。圖39展示比較具有及不具有連續纖維之平行列印試樣的拉伸測試結果。在纖維強化體之情況下，在滑移之前試樣之最大拉伸強度為14.49 MPa，其為不具有纖維之平行試樣之拉伸強度（4.40 MPa）的約三倍。具有及不具有連續纖維之垂直列印試樣的拉伸測試結果展示於圖40中。纖維強化垂直試樣之最大拉伸強度為17.25 MPa，但不具有纖維之試樣僅可達到2.83 MPa。Figures 39 and 40 show strain-stress curves obtained from tensile testing. Under stress, the polysiloxane portion of the specimen remained fully clamped and stretched even under tensile tension and fiber slippage. Figure 39 shows tensile test results comparing parallel printed specimens with and without continuous fibers. In the case of fiber reinforcement, the maximum tensile strength of the specimen before slipping was 14.49 MPa, which was approximately three times the tensile strength of the parallel specimen without fibers (4.40 MPa). Tensile test results for vertically printed specimens with and without continuous fibers are shown in Figure 40. The maximum tensile strength of the fiber-reinforced vertical specimen is 17.25 MPa, but the specimen without fibers can only reach 2.83 MPa.
來自不同列印方向之資料的比較展現，在無纖維強化體之情況下，與在垂直（橫向）方向上列印之試樣相比，在平行（縱向）方向上列印之試樣達到較高拉伸強度及較高極限應變。異向性主要歸因於相鄰列印線及層之間的空隙。在增材製造列印之長絲沈積及堆疊製程期間不可避免地產生某些空隙體積。因此，可得出結論，不同列印方向可能為不同空隙體積分率之結果，其造成某些機械異向性。Comparison of data from different printing directions shows that, in the absence of fiber reinforcement, samples printed in the parallel (longitudinal) direction achieve better results than samples printed in the vertical (transverse) direction. High tensile strength and high ultimate strain. Anisotropy is primarily due to the gaps between adjacent printed lines and layers. Some void volume is inevitably created during the filament deposition and stacking processes for additive manufacturing printing. Therefore, it can be concluded that different printing directions may be the result of different void volume fractions, which cause some mechanical anisotropy.
儘管在不具有纖維強化體之試樣中存在異向性，但具有纖維強化體之垂直試樣能夠提供高達不具有纖維之平行試樣之至多四倍的拉伸強度。因此，儘管不具有纖維之聚矽氧烷試樣在三維增材製造列印部分中展現異向性，但因此可使用纖維強化體來緩解此問題。藉由調整列印複合物中連續纖維之體積比及位向，可控制及最小化異向性效應。另外，可選擇具有不同機械及黏附特性之連續纖維以達成所得複合物之各種異向性比及所需特性。Despite the anisotropy present in specimens without fiber reinforcement, vertical specimens with fiber reinforcement were able to provide up to four times the tensile strength of parallel specimens without fibers. Therefore, although polysiloxane specimens without fibers exhibit anisotropy in the 3D AM printed part, fiber reinforcements can be used to alleviate this problem. By adjusting the volume ratio and orientation of the continuous fibers in the printing composite, anisotropic effects can be controlled and minimized. In addition, continuous fibers with different mechanical and adhesive properties can be selected to achieve various anisotropy ratios and desired properties of the resulting composites.
圖38展示具有以具有長強化纖維之聚矽氧烷列印的額外拉伸試樣。聚矽氧烷擠壓在相對於強化纖維之列印方向平行及垂直方向兩者上定向。展示使用Kevlar™纖維及碳纖維兩者之試樣。在此實施例中，纖維位向方向在拉伸試樣之縱向方向上。然而，如本文別處所提及，強化纖維可經列印，以便相對於擠壓聚矽氧烷之層的方向及列印試樣之縱向或橫向位向在強化層中以任何方向定向。Figure 38 shows additional tensile specimens printed with polysiloxane with long reinforcing fibers. The polysiloxane extrusion is oriented both parallel and perpendicular to the printing direction of the reinforcing fibers. Demonstration of samples using both Kevlar™ fiber and carbon fiber. In this example, the fiber orientation direction is in the longitudinal direction of the tensile specimen. However, as mentioned elsewhere herein, the reinforcing fibers can be printed so as to be oriented in any direction in the reinforcing layer relative to the direction of the layer of extruded polysiloxane and the longitudinal or transverse orientation of the printed sample.
圖38展示（a）在列印平板試樣之縱向方向上延伸之縱向延伸Kevlar®纖維。熱固性含聚矽氧烷聚合物亦在相對於強化纖維層之平行位向上列印，強化纖維層亦在試樣之縱向方向上。在圖38中試樣（b）中，Kevlar®纖維層再次在縱向方向上列印，在此實施例中列印聚矽氧烷層以垂直於強化纖維之位向列印，且列印沿試樣在橫向方向上延伸。圖38在（c）及（d）部分中與圖38（a）及（b）部分分別在相同位向上，但代替Kevlar®強化纖維，在（c）及（d）中使用碳強化纖維。試樣中之各者列印為在橫向方向上量測寬度為18 mm，在縱向方向上量測長度為88.9 mm，其中橫向尺寸及縱向尺寸在x-y平面中，且在垂直於跨試樣之長度及寬度之平面的z方向上量測厚度為1.3 mm。列印纖維絲束，以便在各纖維絲束之間具有2 mm橫向間距。各聚矽氧烷列印層之層高度為0.686 mm，且一個纖維層。Figure 38 shows (a) longitudinally extending Kevlar® fibers extending in the longitudinal direction of a printed flat specimen. The thermosetting polysiloxane-containing polymer also prints upward parallel to the reinforcing fiber layer, which is also in the longitudinal direction of the specimen. In sample (b) in Figure 38, the Kevlar® fiber layer is again printed in the longitudinal direction. In this example, the polysiloxane layer is printed perpendicular to the orientation of the reinforcing fibers, and the printing is along the The specimen extends in the transverse direction. Parts (c) and (d) of Figure 38 are in the same orientation as parts (a) and (b) of Figure 38, respectively, but instead of Kevlar® reinforced fibers, carbon reinforced fibers are used in (c) and (d). Each of the specimens is printed with a width measured in the transverse direction of 18 mm and a length of 88.9 mm measured in the longitudinal direction, where the transverse and longitudinal dimensions are in the x-y plane and are normal to the span across the specimen. The thickness measured in the z-direction of the plane of length and width is 1.3 mm. Print the fiber tows so that there is 2 mm lateral spacing between fiber tows. The layer height of each polysiloxane printing layer is 0.686 mm, and there is one fiber layer.
圖38展示如上文所提及之經克維拉纖維絲束或碳纖維絲束強化之平板形式的列印聚矽氧烷試樣之照片影像，其中針對各類型之纖維在列印之縱向（平行）及橫向（垂直）方向上且相對於在試樣之增材列印期間在縱向方向上鋪設之纖維列印聚矽氧烷。Figure 38 shows photographic images of printed polysiloxane samples in the form of flat sheets reinforced with Kevlar fiber tows or carbon fiber tows as mentioned above, with each type of fiber in the longitudinal direction of the printing (parallel to ) and in the transverse (vertical) direction and relative to the fiber-printed polysiloxane laid in the longitudinal direction during additive printing of the specimen.
以下展示之拉伸資料在纖維方向上獲取。圖43及44展示來自圖38中之拉伸試樣（試樣（a）、（b）、（c）及（d）））的應力-應變曲線。如圖43-44中可觀測到，樣品在20%與150%伸長率之間的低延伸下展示高應力（在10與18 MPa之間）。此時，樣品屈服，且纖維開始在聚矽氧烷基質中滑移。高於150%至200%伸長率之曲線的高延伸部分說明在纖維經歷滑移之後聚矽氧烷基質拉伸的效果。克維拉及碳纖維絲束兩者展示類似行為及滑移。可以多種方式減少或最小化纖維絲束滑移，包括在纖維上使用上膠劑、如本揭示案上文所描述之共擠壓至纖維上、經設計界面化學、聚矽氧烷官能化或纖維上之任何上膠或塗層、界面或基質交聯、使用黏著劑或幫助將聚矽氧烷基質更緊密地黏合至纖維絲束之其他策略。The tensile data shown below were obtained in the fiber direction. Figures 43 and 44 show stress-strain curves from the tensile specimens in Figure 38 (specimens (a), (b), (c) and (d)). As can be observed in Figures 43-44, the samples exhibit high stresses (between 10 and 18 MPa) at low extensions between 20% and 150% elongation. At this point, the sample yields and the fibers begin to slip in the polysiloxane matrix. The high extension portion of the curve above 150% to 200% elongation illustrates the effect of stretching of the polysiloxane matrix after the fibers experience slip. Both Kevlar and carbon fiber tows exhibit similar behavior and slip. Fiber tow slip can be reduced or minimized in a variety of ways, including using sizing agents on the fibers, coextrusion onto the fibers as described above in this disclosure, engineered interfacial chemistry, polysiloxane functionalization, or Any sizing or coating on the fibers, interfacial or matrix cross-linking, use of adhesives, or other strategies to help bond the polysiloxane matrix more tightly to the fiber tows.
圖41展示使用在此實施例中描述之設備及如上文提及之條件三維列印纖維強化聚矽氧烷環的實例。圖42A-42D繪示具有長纖維強化體之彎曲管的三維模型（圖42A）以及使用此實施例中所描述之設備列印之三維列印物體的頂部視圖（圖42B）及左端及右端視圖（分別為圖42C及42D）。可類似地列印其他形狀及組態。Figure 41 shows an example of three-dimensional printing of fiber-reinforced polysiloxane rings using the equipment described in this example and conditions as mentioned above. Figures 42A-42D illustrate a three-dimensional model of a curved tube with long fiber reinforcement (Figure 42A) and a top view (Figure 42B) and left and right end views of a three-dimensional printed object printed using the apparatus described in this example. (Figures 42C and 42D respectively). Other shapes and configurations can be printed similarly.
實施例6：鑑別使用聚矽氧烷進行的物件之較佳三維增材製造列印的關鍵因素Example 6: Key factors identifying optimal 3D additive manufacturing printing of objects using polysiloxane
作為此實施例之一部分，本申請人藉由在零剪切速率下使用高黏度且在高剪切速率下使用低黏度以評估黏度對列印之影響，以鑑別較佳含矽聚合物之較佳參數，亦即，列印聚矽氧烷同時使用聚矽氧烷達成具有所需特性之較佳列印物件。樣品A（Dow Xiameter™ RBL 2004-50聚矽氧烷）以10/s至950/s範圍內之速率剪切，且量測對應表觀黏度資料。對數種聚矽氧烷進行類似實驗，包括樣品B（Elkem 20501-50）及樣品C（每100重量份總彈性體50重量份Xiameter™ RBL 2004-50 A部分聚矽氧烷及50重量份Xiameter™ 2004-50 B部分聚矽氧烷之混合共混物，且包括每100重量份總彈性體3份Evonik Aerosil® R972以對Xiameter聚矽氧烷之賓漢塑膠行為進行改質）。此資料展示於圖47中，作為剪切速率相對於樣品A-C之表觀黏度的圖示，該資料經外推以獲得樣品A-C在零剪切速率下之表觀黏度。As part of this example, the Applicants evaluated the effect of viscosity on printing to identify better silicon-containing polymers by using high viscosity at zero shear rate and low viscosity at high shear rate. Optimum parameters, that is, printing polysiloxane while using polysiloxane to achieve better printed objects with required characteristics. Sample A (Dow Xiameter™ RBL 2004-50 polysiloxane) was sheared at a rate ranging from 10/s to 950/s, and the corresponding apparent viscosity data was measured. Similar experiments were conducted on several polysiloxanes, including Sample B (Elkem 20501-50) and Sample C (50 parts by weight Xiameter™ RBL 2004-50 Part A polysiloxane and 50 parts by weight Xiameter per 100 parts by weight total elastomer ™ 2004-50 Part B polysiloxane hybrid blend and includes 3 parts Evonik Aerosil® R972 per 100 parts by weight total elastomer to modify the Bingham plastic behavior of Xiameter polysiloxane). This data is presented in Figure 47 as a plot of shear rate versus apparent viscosity of Samples A-C, which was extrapolated to obtain the apparent viscosity of Samples A-C at zero shear rate.
為鑑別用於達成所需增材製造列印寬容度之較佳施加壓力範圍，進行進一步評估。較佳具有寬增材製造列印速度範圍以列印來自各種聚矽氧烷之物件。舉例而言，單組分過氧化物可固化聚矽氧烷Primetech™ AMS 3302H在大於約100,000泊之極高零剪切黏度下展現極佳形狀保持。然而，相同聚矽氧烷展現極差的剪切稀化，且因此即使在施加約120 psi之高壓時，該材料之列印速度亦小於1 mm/s。相比之下，樣品D中之雙組分鉑可固化聚矽氧烷（Dow SE-1700）具有可藉由將壓力自約2 psi增加至約15 psi而自約2 mm/s之低列印速度快速增加至約70 mm/s之高列印速度的列印速度。如圖48中所示，藉由在20至100 psi範圍內增加壓力，所測試之其他雙組分聚矽氧烷，諸如上文提及之樣品A-C，亦具有約2毫米/秒至70毫米/秒之寬列印速度範圍。Further evaluation was performed to identify the optimal applied pressure range to achieve the desired AM printing latitude. Better to have a wide additive manufacturing print speed range to print objects from a variety of polysiloxanes. For example, the one-component peroxide curable polysiloxane Primetech™ AMS 3302H exhibits excellent shape retention at very high zero-shear viscosities of greater than approximately 100,000 poise. However, the same polysiloxane exhibits extremely poor shear thinning, and therefore the material prints at less than 1 mm/s even when high pressures of about 120 psi are applied. In comparison, the two-component platinum-curable polysiloxane (Dow SE-1700) in Sample D has a low range of about 2 mm/s by increasing the pressure from about 2 psi to about 15 psi. The printing speed quickly increases to a high printing speed of about 70 mm/s. As shown in Figure 48, by increasing the pressure in the range of 20 to 100 psi, other two-component polysiloxanes tested, such as Samples A-C mentioned above, also had from about 2 mm/sec to 70 mm /sec wide print speed range.
所屬技術領域中具有通常知識者應瞭解，在不脫離本發明之廣泛發明概念之情況下，可對上述具體實例作出改變。因此，應理解，本發明不限於所揭示之特定具體實例，但預期涵蓋所附申請專利範圍所限定之本發明精神及範圍內之修改。It will be understood by those of ordinary skill in the art that changes may be made in the specific examples described above without departing from the broad inventive concept of the invention. It is, therefore, to be understood that this invention is not limited to the particular examples disclosed, but it is intended to cover modifications within the spirit and scope of the invention as defined by the appended claims.
當結合附圖閱讀時，將更佳地理解前文發明內容以及下文較佳具體實例之實施方式。出於說明本發明之目的，在圖式中示出目前較佳之具體實例。然而，應理解本發明並不限於所示的確切配置及工具。本文中包括至少一個彩製圖式。在申請且支付必要費用後，專利局將提供具有彩色圖式之本專利或專利申請公開案之複本。在圖式中: The foregoing summary of the invention and the following preferred embodiments will be better understood when read in conjunction with the accompanying drawings. For the purpose of illustrating the invention, presently preferred specific examples are shown in the drawings. It should be understood, however, that this invention is not limited to the exact arrangements and instrumentalities shown. This article contains at least one drawing illustrated in color. Upon application and payment of the necessary fee, the Patent Office will provide a copy of this patent or patent application publication with color drawing. In the diagram:
[圖1]為用於本文中之方法之具體實例中的設備之正面透視示意圖；[Fig. 1] is a schematic front perspective view of an apparatus used in a specific example of the method herein;
[圖1A]為圖1之設備的正面透視圖；[Fig. 1A] is a front perspective view of the device of Fig. 1;
[圖2]為用於圖1之設備中的列印噴嘴及安裝臂之放大的正面透視圖；[Figure 2] is an enlarged front perspective view of the printing nozzle and mounting arm used in the device of Figure 1;
[圖3]為圖2之列印噴嘴及安裝臂之放大的正面正視圖；[Figure 3] is an enlarged front view of the printing nozzle and mounting arm of Figure 2;
[圖4]為圖2之噴嘴及安裝臂之放大的俯視正視圖；[Figure 4] is an enlarged top front view of the nozzle and mounting arm of Figure 2;
[圖5]為圖2之噴嘴及安裝臂之右側正視圖；[Figure 5] is a right side front view of the nozzle and mounting arm in Figure 2;
[圖6]為圖2之安裝臂的正面透視圖；[Figure 6] is a front perspective view of the mounting arm of Figure 2;
[圖7]為圖6之安裝臂之右側正視圖；[Figure 7] is a front view of the right side of the mounting arm of Figure 6;
[圖8]為圖6之安裝臂之正面正視圖；[Figure 8] is a front view of the mounting arm of Figure 6;
[圖9]為圖6之安裝臂之俯視正視圖；[Figure 9] is a top front view of the mounting arm of Figure 6;
[圖10]為圖3之列印噴嘴及安裝臂之左側正視圖；[Figure 10] is a left side front view of the printing nozzle and mounting arm in Figure 3;
[圖11]為沿著線11-11截取之圖10之列印噴嘴及安裝臂的縱向橫截面圖；[Fig. 11] is a longitudinal cross-sectional view of the printing nozzle and mounting arm of Fig. 10 taken along line 11-11;
[圖12]為用於圖1之設備中之熱塑性擠壓機頭及噴嘴及安裝臂整件的正面透視圖；[Figure 12] is a front perspective view of the entire thermoplastic extrusion head, nozzle, and mounting arm used in the equipment of Figure 1;
[圖13]為圖12之整件之仰視透視圖；[Fig. 13] is a bottom perspective view of the entire piece of Fig. 12;
[圖14]為圖12之整件之後面透視圖；[Fig. 14] is a rear perspective view of the entire unit in Fig. 12;
[圖15]為使用圖1之設備進行增材列印的製程流程圖；[Figure 15] is a process flow chart for additive printing using the equipment in Figure 1;
[圖16]為使用圖1之設備以及在本文中利用嵌入型耐綸網格設計層及聚矽氧烷的方法形成之實例複合零件的照片圖示；[Fig. 16] A photographic illustration of an example composite part formed using the equipment of Fig. 1 and the method herein utilizing an embedded nylon mesh design layer and polysiloxane;
[圖17]為列印製程中之複合物件之照片圖示，展示在聚矽氧烷之部分層下的網格耐綸層；[Figure 17] is a photographic illustration of a composite object during the printing process, showing a mesh nylon layer under a partial layer of polysiloxane;
[圖18]為完成的複合物件之照片圖示，展示經由聚矽氧烷層看見之暗網格；[Figure 18] is a photographic illustration of the completed composite object, showing the dark grid seen through the polysiloxane layer;
[圖19]為具有聚矽氧烷層（白色）及丙烯腈-丁二烯-苯乙烯（ABS）層（黑色）作為強化層的經列印之聚矽氧烷及ABS複合物件的照片圖示；[Figure 19] is a photograph of a printed polysiloxane and ABS composite object with a polysiloxane layer (white) and an acrylonitrile-butadiene-styrene (ABS) layer (black) as a reinforcing layer. Show;
[圖20]為毛細管流變儀資料之圖示，亦即用於評估用於評估列印之材料之黏度範圍的本文中之實施例在不同溫度下使用的聚矽氧烷聚合物的表觀剪切黏度（以Pa-s為單位）對比剪切速率（1/s）之間之關係；[Figure 20] is a graphical representation of capillary rheometer data, i.e., the appearance of polysiloxane polymers used in the examples herein at different temperatures used to evaluate the viscosity range of materials used to evaluate printing. The relationship between shear viscosity (in Pa-s) and shear rate (1/s);
[圖21]為在本文中之實施例中在分層複合物中使用聚矽氧烷及耐綸長絲層形成之三維管狀複合物件的照片影像；[Figure 21] is a photographic image of a three-dimensional tubular composite object formed using layers of polysiloxane and nylon filaments in a layered composite in the embodiments herein;
[圖21A]包括圖21中之樣品的SEM圖示；[Fig. 21A] A SEM diagram including the sample in Fig. 21;
[圖22]為用於在用於測試之三層平坦複合物件中量測內層黏附之剝離測試的圖示；[Figure 22] Illustration of the peel test used to measure inner layer adhesion in the three-layer flat composite article used for testing;
[圖22A]為本文中之實施例中所用之測試機器的正面透視圖；[Fig. 22A] is a front perspective view of the test machine used in the embodiments herein;
[圖23A]為使用0-20-340耐綸6,6網格強化層與聚矽氧烷層形成之複合物件的照片圖示；[Figure 23A] is a photographic illustration of a composite object formed using a 0-20-340 nylon 6,6 mesh reinforcement layer and a polysiloxane layer;
[圖23B]為使用三角形耐綸6.6耐綸6,6網格強化層與聚矽氧烷層形成之複合物件的照片圖示；[Figure 23B] is a photographic illustration of a composite object formed using a triangular nylon 6.6 nylon 6,6 mesh reinforcement layer and a polysiloxane layer;
[圖24A]為使用耐綸6,6及聚矽氧烷層形成之呈O型環形式之複合物件的照片圖示；[Figure 24A] is a photographic illustration of a composite object in the form of an O-ring formed using nylon 6,6 and polysiloxane layers;
[圖24B]為使用耐綸6,6及聚矽氧烷層形成之複雜的三維複合物件；[Figure 24B] is a complex three-dimensional composite object formed using nylon 6,6 and polysiloxane layers;
[圖25]為實施例4中所用之來自SolidWorks®之三維模型的代表性螢幕捕獲；[Figure 25] is a representative screen capture of the 3D model from SolidWorks® used in Example 4;
[圖26]為.STL格式檔案之實例，展示鑑別為CM之彎曲模型與鑑別為ES之導出的.STL模型之間之差異以解釋本文中之實施例4中的列印程序；[Figure 26] is an example of a .STL format file, showing the difference between the curved model identified as CM and the derived .STL model identified as ES to explain the printing process in Embodiment 4 of this article;
[圖27]為Cura™ LulzBot™ 3.6.20介面之螢幕截圖的代表性實例；[Figure 27] is a representative example of a screenshot of the Cura™ LulzBot™ 3.6.20 interface;
[圖28]為與本文中之實施例4中所用之列印機相關聯的軟體中所採用的G代碼之若干行的實例；[Fig. 28] is an example of several lines of G code used in the software associated with the printer used in Embodiment 4 of this article;
[圖29]為使用本文中之實施例4中之程序列印之管狀物品的俯視平面圖及照片影像，展示強化TPU之內部殼（紅色）及聚矽氧烷之外部殼（白色）；[Figure 29] is a top plan view and photographic image of a tubular article printed using the program in Example 4 of this article, showing the inner shell of reinforced TPU (red) and the outer shell of polysiloxane (white);
[圖30]為圖29之管狀物品的透視圖。[Fig. 30] is a perspective view of the tubular article of Fig. 29. [Fig.
[圖31]為用於本文中方法之在另一具體實例中之列印設備的正面正視圖，該列印設備用於經由第一噴嘴列印組成物（諸如包括熱固性聚矽氧烷聚合物之組成物）及用包括纖維切割裝置之第二噴嘴列印長強化纖維；[FIG. 31] is a front elevation view of a printing apparatus for printing a composition, such as a composition including a thermosetting polysiloxane polymer, via a first nozzle, in another embodiment of the method herein. composition) and printing long reinforcing fibers using a second nozzle including a fiber cutting device;
[圖32]為圖31之設備的透視圖；[Fig. 32] is a perspective view of the device of Fig. 31;
[圖33]為用於圖31之設備中的安裝臂、兩個列印機構及纖維切割裝置之整件的俯視透視圖；[Fig. 33] is a top perspective view of the entire mounting arm, two printing mechanisms and fiber cutting device used in the apparatus of Fig. 31;
[圖34]為圖33之整件的仰視透視圖；[Fig. 34] is a bottom perspective view of the entire piece of Fig. 33;
[圖35A]為可拆卸附接之切割裝置整件的俯視正面透視圖；[Fig. 35A] is a top front perspective view of the entire removably attached cutting device;
[圖35B]為圖35A之切割裝置整件的仰視正面透視圖；[Figure 35B] is a bottom front perspective view of the entire cutting device of Figure 35A;
[圖35C]為圖35A之切割裝置整件的俯視後面透視圖；[Fig. 35C] is a top rear perspective view of the entire cutting device of Fig. 35A;
[圖35D]為圖35A之切割裝置整件的仰視後面透視圖；[Fig. 35D] is a bottom rear perspective view of the entire cutting device of Fig. 35A;
[圖35E]為圖35A之切割裝置整件的側面正視圖；[Fig. 35E] is a side elevation view of the entire cutting device of Fig. 35A;
[圖36]為用於諸如圖35A-35E之切割裝置整件的切割裝置之一具體實例的示意性透視圖；[FIG. 36] is a schematic perspective view of a specific example of a cutting device for an integral part of the cutting device such as FIGS. 35A-35E;
[圖37]為圖31之設備的內部放大視圖，該設備在長強化纖維列印機構之一部分中具有管支撐件，諸如聚四氟乙烯（polytetrafluoroethylene；PTFE）管支撐件，用於連續纖維穿過長纖維列印機構至其列印噴嘴；[Fig. 37] is an enlarged internal view of the apparatus of Fig. 31, which has a tube support, such as a polytetrafluoroethylene (PTFE) tube support, in a part of the long reinforced fiber printing mechanism for continuous fiber threading Too long fiber printing mechanism to its printing nozzle;
[圖37A]為圖37中所示之第二噴嘴的正面透視圖；[Fig. 37A] is a front perspective view of the second nozzle shown in Fig. 37;
[圖37B]為圖37中所示之第二噴嘴的正面正視圖；[Fig. 37B] is a front elevation view of the second nozzle shown in Fig. 37;
[圖37C]為圖37中所示之第二噴嘴的後面正視圖；[Fig. 37C] is a rear front view of the second nozzle shown in Fig. 37;
[圖37D]為圖37中所示之第二噴嘴的後面透視圖；[Fig. 37D] is a rear perspective view of the second nozzle shown in Fig. 37;
[圖38]為實施例5中列印之列印複合物試樣照片圖示，其包括（a）與列印Kevlar®長強化纖維呈平行位向的熱固性聚矽氧烷之列印複合物；（b）與列印Kevlar®長強化纖維呈垂直位向的熱固性聚矽氧烷之列印複合物；（c）與列印碳長強化纖維呈平行位向的熱固性聚矽氧烷之列印複合物；及（d）與列印碳長強化纖維呈垂直位向的熱固性聚矽氧烷之列印複合物；[Figure 38] is a photographic illustration of the printed composite sample printed in Example 5, which includes (a) a printed composite of thermosetting polysiloxane with a parallel orientation to the printed Kevlar® long reinforcing fibers. ; (b) A printed composite of thermosetting polysiloxane with a perpendicular orientation to the printed Kevlar® long reinforcing fibers; (c) A thermosetting polysiloxane with a parallel orientation to the printed carbon long reinforcing fibers printing composite; and (d) a printing composite of thermosetting polysiloxane in a perpendicular orientation to the printing carbon long reinforcing fibers;
[圖38A]為在以下情況下列印之來自實施例5之其他列印複合物試樣的照片圖示：（a）垂直方向，無長強化纖維；（b）垂直方向，長強化纖維層在縱向方向上延伸；（c）平行方向，無長強化纖維；及（d）平行方向，長強化纖維層亦在縱向方向上延伸；[Figure 38A] is a photographic illustration of other printed composite samples from Example 5 printed under the following conditions: (a) vertical direction, without long reinforcing fibers; (b) vertical direction, long reinforcing fiber layers at Extending in the longitudinal direction; (c) parallel direction, no long reinforcing fibers; and (d) parallel direction, long reinforcing fiber layers also extending in the longitudinal direction;
[圖39]為展示拉伸應力與應變之關係的圖示，以說明使用如圖38A中之樣品在具有及不具有碳纖維層的情況下，與在縱向方向上列印之聚矽氧烷材料的增材列印複合物相比，在縱向方向上列印之增材列印聚矽氧烷材料的拉伸強度。[Figure 39] is a graph showing the relationship between tensile stress and strain to illustrate the use of the sample as shown in Figure 38A with and without a carbon fiber layer and a polysiloxane material printed in the longitudinal direction. The tensile strength of additively printed composites compared to additively printed polysiloxane materials printed in the longitudinal direction.
[圖40]為展示拉伸應力與應變之關係的圖示，以說明與碳纖維及聚矽氧烷材料之增材列印複合物相比在橫向方向上列印之增材列印聚矽氧烷材料的拉伸強度，在增材列印複合物中，聚矽氧烷材料在橫向位向上列印且碳纖維層在縱向方向上列印，使得在複合物中碳纖維與聚矽氧烷列印層具有垂直位向，如在圖38A之樣品中。[Figure 40] A diagram showing the relationship between tensile stress and strain to illustrate the ability of additively printed polysiloxane to print in the transverse direction compared to additively printed composites of carbon fiber and polysiloxane materials. The tensile strength of the alkane material. In the additive printing composite, the polysiloxane material prints in the transverse direction and the carbon fiber layer prints in the longitudinal direction, so that the carbon fiber and polysiloxane print in the composite. The layers have a vertical orientation, as in the sample of Figure 38A.
[圖41]為本文實施例5中增材列印之圓盤狀碳纖維強化聚矽氧烷複合零件的照片圖示；[Figure 41] is a photographic illustration of the additively printed disc-shaped carbon fiber reinforced polysiloxane composite part in Example 5 of this article;
[圖41A]為表示用於使用本文所描述之方法及設備列印之彎曲圓柱形碳纖維強化聚矽氧烷複合零件之設計模型的代表性圖示；[Figure 41A] is a representative diagram showing a design model of a curved cylindrical carbon fiber reinforced polysiloxane composite part printed using the methods and equipment described herein;
[圖42B]為在本文實施例5中使用圖41A之設計增材列印之彎曲圓柱形碳纖維強化聚矽氧烷複合零件之俯視圖的照片圖示；[Figure 42B] is a photographic illustration of a top view of a curved cylindrical carbon fiber reinforced polysiloxane composite part additively printed using the design of Figure 41A in Example 5 of this article;
[圖42C]為圖42B之複合零件之左端視圖的照片圖示；[Fig. 42C] is a photographic illustration of the left end view of the composite part of Fig. 42B;
[圖42D]為圖42B之複合零件之右端視圖的照片圖示；[Fig. 42D] is a photographic illustration of the right end view of the composite part of Fig. 42B;
[圖43]為兩個樣品之應力對應變之圖示，樣品中之各者為聚矽氧烷及Kevlar®長強化纖維之增材列印平板複合物，其中聚矽氧烷垂直於以及平行於縱向延伸穿過平板之長強化纖維方向列印；[Figure 43] is a graphical representation of stress versus strain for two samples, each of which is an additively printed flatbed composite of polysiloxane and Kevlar® long reinforcement fibers, where the polysiloxane is perpendicular to and parallel to Print in the direction of long reinforcing fibers extending longitudinally across the slab;
[圖44]為兩個樣品之應力對應變之圖示，樣品中之各者為聚矽氧烷及碳長強化纖維之增材列印平板複合物，其中聚矽氧烷垂直於以及平行於縱向延伸穿過平板之長強化纖維方向列印；[Figure 44] is a graphical representation of stress versus strain for two samples, each of which is an additively printed flat sheet composite of polysiloxane and long carbon reinforced fibers, where the polysiloxane is perpendicular to and parallel to Directional printing of long reinforcing fibers extending longitudinally across the slab;
[圖45]為用於操作切割裝置及用於饋入連續長纖維之控制系統的控制電路之示意性圖示；[Fig. 45] is a schematic illustration of a control circuit for operating a cutting device and a control system for feeding continuous filaments;
[圖46]為用於將切割裝置整合至本文具體實例之列印操作中提供擠壓長連續纖維以形成複合物件之列印操作步驟的流程圖；[Fig. 46] is a flow chart for integrating a cutting device into a printing operation of embodiments herein to provide printing operation steps for extruding long continuous fibers to form composite objects;
[圖47]為根據實施例6之樣品A-C中各種聚矽氧烷材料隨剪切速率而變之表觀黏度的圖示；及 [圖48]為根據實施例6中樣品A-D隨施加至第一加壓噴嘴之壓力而變之擠壓速度的圖示。 [Figure 47] is a graphical representation of the apparent viscosity of various polysiloxane materials as a function of shear rate in Samples A-C according to Example 6; and [Fig. 48] is a graph showing the extrusion speed of samples A-D according to the pressure applied to the first pressurizing nozzle according to Example 6.
102:支架整件 102: The whole bracket
108:支撐框架 108:Support frame
112:基板 112:Substrate
114:噴嘴整件 114: Complete nozzle
118:可滑動構件 118:Slidable member
120:控制器 120:Controller
124:加壓源 124: Pressurized source
125:管 125:Tube
126:第一噴嘴 126:First nozzle
130:第二噴嘴 130:Second nozzle
132:列印機驅動機構 132:Printer drive mechanism
134:增材製造列印機 134:Additive Manufacturing Printer
150:噴嘴出口 150:Nozzle outlet
154:噴嘴擠壓機尖端 154:Nozzle extruder tip
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