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Plastisol

Plastisol is a type of vinyl compound consisting of fine (PVC) particles suspended in a , typically in a 50/50 weight ratio, which remains stable at and undergoes irreversible curing upon heating to form a flexible, solid material. This process, known as gelation and fusion, occurs as the PVC particles absorb the and swell when heated, typically between 100–175°C for 10–90 minutes, resulting in a thermoset-like product with properties such as hardness ranging from 30A to 55A. The composition of plastisols generally includes PVC resin with k-values of 59–86, plasticizers like di(2-ethylhexyl) phthalate (DOP), and various additives such as stabilizers, pigments, fillers (e.g., at 10–40 parts per hundred resin), and diluents to tailor , color, and other characteristics. Rheological are critical, with viscosities often below 10,000 centipoise, enabling easy via methods like , dipping, spraying, or , while thermal involve gelation around the PVC temperature and full fusion at approximately 190°C. attributes, including tensile strength and , depend on factors like resin blending, filler content, and curing conditions, with minimal shrinkage of about 2% during . Plastisols find widespread applications in industries requiring flexible, durable coatings and moldings, such as automotive underbody sealers, seam sealers for resistance and noise suppression, carpet backing, production, and toys or gloves due to their low-cost tooling and customizable formulations. Their development traces back to 1926 when Waldo Semon invented plasticized PVC, with PVC plastisol molding applications expanding in the late as a versatile, solvent-free alternative for creating lightweight, adherent surfaces without blistering issues common in solvent-based systems. Advantages include high solids content (100%), environmental benefits from reduced volatile emissions, and adaptability for additive manufacturing techniques like for soft, ductile parts.

Definition and Properties

Composition

Plastisol is a colloidal consisting of fine (PVC) particles suspended in a , forming a stable, solvent-free formulation suitable for various applications. The PVC particles, typically derived from , have sizes ranging from 0.5 to 2.0 micrometers, enabling effective and subsequent processing without aggregation at . This ensures the mixture remains fluid, with the acting as the continuous phase that coats and solvates the discrete PVC domains upon activation. Common plasticizers in plastisol formulations include such as (DINP) and dioctyl phthalate (DOP), as well as adipates like (DOA) and sebacates such as dibutyl sebacate, selected for their compatibility with PVC and ability to impart flexibility. The plasticizer content typically ranges from 50 to 100 parts per hundred resin (phr), corresponding to approximately 33% to 50% by weight of the total formulation, though higher levels up to around 70% by weight can be used for enhanced softness and low-temperature performance. Additives are incorporated to tailor the composition for , , and . Heat stabilizers, such as calcium-zinc systems, prevent degradation during processing, while secondary stabilizers like enhance long-term performance. Pigments, including for opacity or for coloration, are added for visual properties, and fillers like serve to adjust , reduce cost, and improve mechanical reinforcement without significantly altering the core dispersion. During curing, the PVC particles absorb the when heated above the temperature, leading to swelling, gelation around 120°C, and eventual coalescence into a homogeneous, fused solid by approximately 190°C, without involving chemical reactions. This physical transformation relies on the intimate mixing of components in the initial , resulting in a flexible, material.

Physical and Chemical Properties

Plastisols exhibit distinct thermal properties that enable their processing into flexible solids. At , they remain as a stable , but upon heating to approximately 140–160°C, initial gelation occurs through the absorption of by PVC particles, leading to a viscous state. Full typically requires temperatures of 170–200°C, where particle completes, forming a coherent . Upon cooling below 60°C, the fused solidifies into a flexible, rubbery solid with Shore A ranging from 30 to 90, depending on the content. The rheological behavior of plastisols is characterized by at ambient temperatures typically in the range of 1,000 to 50,000 , giving them a paste-like suitable for applications such as and molding. They display thixotropic properties, where decreases under applied , facilitating during , and exhibit pseudoplastic , allowing recovery of structure upon cessation of . At higher shear rates, some formulations may show dilatancy, though this is less common in standard compositions. Post-curing, plastisols demonstrate excellent , remaining inert to and resistant to many acids and alkalis, which contributes to their durability in harsh environments. They are pH neutral and have a of 1.1–1.4 g/cm³, providing a balanced weight for various uses. Additionally, cured plastisols are highly compatible with pigments, enabling the creation of opaque, vibrant colors without bleeding or migration. In comparison to related materials, plastisols differ from dry PVC powders by being a ready-to-use , eliminating the need for on-site mixing with plasticizers. Unlike organosols, which incorporate volatile solvents to reduce , plastisols contain no such volatiles, thereby minimizing emissions during application and curing.

Production

Manufacturing Process

The manufacturing process of plastisol primarily involves creating a stable colloidal dispersion of fine (PVC) particles in a through controlled high-shear mixing. This batch operation ensures the resin particles are uniformly wetted and suspended without or premature gelation, relying on the partial of plasticizer into the porous resin structure. The process typically starts with pre-blending dry PVC resin—either emulsion-grade (fine particles, 0.2–2 µm) or suspension-grade—with stabilizers, pigments, and fillers in a low-speed to achieve homogeneity. Liquid is then added gradually under to minimize air entrapment, using jacketed high-shear equipment such as planetary mixers, dissolvers, or turbosphere units (e.g., 200-liter pilot-scale vessels with ). Mixing occurs at speeds of 1,000–3,000 RPM for initial (2–5 minutes), followed by additional mixing for 10–30 minutes at 20–50°C to promote uniform particle while controlling heat buildup. Deaeration follows under (25–27 inches ) for 5–30 minutes to remove entrained air, yielding a viscous, lump-free paste ready for storage or use. Throughout, is monitored via cooling jackets to prevent or gelling. involves testing with a Brookfield (target 1,000–5,000 at 25°C, spindle RV-4 at 20 rpm), via for uniformity, and gelation (140–160°C) to confirm batch consistency and performance. Scale-up from batches (1–10 kg) to (tons) employs larger blenders or planetary mixers, with energy input regulated to preserve and rheological properties across volumes.

Formulations and Variations

Plastisols can be adapted through various formulations to meet specific performance needs, such as altered , curing temperatures, mechanical properties, or environmental compliance, while maintaining the base of PVC in plasticizers. These variations typically involve adjusting additive ratios or incorporating modifiers, ensuring compatibility with the core PVC-plasticizer for uniform during heat processing. Organosols represent a key variation where plastisols are diluted with volatile solvents to significantly reduce , enabling applications like spraying or thin- . These solvents, often spirits comprising mixtures of cycloaliphatic, linear, and branched paraffinic hydrocarbons, are incorporated at 5-55 wt% of the total liquid phase, with lower plasticizer levels to prevent excessive of the PVC. During curing, the solvents evaporate, leaving a fused PVC- similar to standard plastisols. This formulation enhances coatability on substrates but requires careful solvent selection to avoid premature solidification. High-heat or low-temperature variants modify the standard curing range of 150-210°C by incorporating or modifiers, or specialized plasticizers, to achieve at 120-150°C for heat-sensitive uses, or enhanced stability above 200°C for demanding environments. modifiers, such as or proprietary blends like Mod-Epox, reduce and improve efficiency at lower temperatures while boosting thermal resistance in high-heat formulations. modifiers further aid in low-temperature curing by promoting cross-linking, allowing gelation below 130°C without compromising flexibility. Plasticizers like adipates (e.g., ) contribute to low-temperature flexibility, while trimellitates (e.g., trioctyl trimellitate) enhance heat and extraction resistance in elevated-temperature variants. Filled plastisols incorporate inert materials like silica or at 20-50 phr (parts per hundred resin) to lower costs, increase , and modify properties such as tensile strength and hardness. acts as a primary extender, improving opacity and rigidity while maintaining processability, whereas silica enhances and but can raise if not balanced with plasticizers. These fillers, typically 10-30 wt% of the total , reduce expenses without severely impacting flexibility when limited to moderate loadings, though higher amounts (up to 50 phr) may require stabilizers like . Custom blends address regulatory and sustainability demands, such as phthalate-free options using bio-based or alternative plasticizers like citrates or at 40-100 phr to replace traditional (e.g., DINP or ). These formulations ensure comparable flexibility and durability while complying with restrictions on in consumer products. Viscosity can be fine-tuned by selecting resin grades with finer particle sizes (0.2-1 µm) for smoother flow and lower shear rates, or porous resins for faster plasticizer absorption, targeting 1,000-5,000 cP for optimal handling.

History

Origins and Early Development

Plastisol, a suspension of (PVC) particles in a , originated from research aimed at creating flexible, solvent-free alternatives to traditional lacquers and rubber coatings. In 1926, Waldo L. Semon, a chemist at B.F. Goodrich (now part of Avient, formerly PolyOne), discovered the plasticization of PVC while experimenting with ways to make the brittle more workable, initially blending it with additives like tritolyl to produce flexible materials without dissolving the resin. This breakthrough addressed the challenges of PVC's rigidity and thermal instability, which had limited its practical use since its in the early 1900s. Semon's work focused on developing corrosion-resistant coatings, leading to early formulations for lining metal storage tanks and other industrial applications. Early patents formalized these innovations, with Semon's U.S. Patent 2,188,396 (issued January 30, 1940) describing a method for preparing PVC compositions using paste resins dispersed in plasticizers, enabling processes like spreading and shaping without prior heating. This patent emphasized dip-coating techniques, initially applied to produce gloves, toys, and protective coverings, as a solvent-free alternative to volatile organic compounds in lacquers. Commercial-scale production was hindered before 1950 due to difficulties in synthesizing consistent, high-quality PVC resins, with B.F. Goodrich's first dedicated PVC plant operational only in 1940 at Niagara Falls, New York, followed by expansion in 1942. These limitations confined early development to laboratory and limited industrial trials, primarily for wire insulation and coated fabrics under the Koroseal trademark introduced in the 1930s. Post-World War II advancements accelerated plastisol research, particularly in the when the Atlantic Research Corporation explored its binder properties for composite materials in applications. In 1950, ARC tested the first PVC plastisol propellants, combining PVC with and oxidizers to create stable, castable solid fuels, marking a shift toward high-performance uses in rocketry. This work built on wartime needs for rubber substitutes, leveraging plastisol's ability to form durable, flexible matrices upon heating. By the early , improved PVC enabled broader adoption in products, such as coated textiles and molded items, though significant commercialization occurred later.

Commercial Expansion

The commercial expansion of plastisol accelerated in the 1960s and 1970s, driven by its adoption in the toy industry and inks. Plastisol's low-cost production and capacity for vibrant, opaque colors enabled widespread use in flexible toys, such as dolls and figurines, supporting mass-market products during this era of consumer growth. In , the introduction of plastisol inks revolutionized textile decoration by allowing thicker applications, multi-layer designs, and high-speed production without screen clogging, leading to a surge in popularity among commercial printers. By the 1970s, global plastisol production had scaled to thousands of tons annually, fueled by these applications and the broader rise in synthetic materials demand. From the to the , regulatory scrutiny on phthalate plasticizers prompted industry-wide reformulations to safer alternatives, adapting plastisol formulations while maintaining . This period also marked into sectors, including automotive applications where plastisol coatings and provided durable, flexible barriers against and in components like and underbody protections. Growth in further diversified markets, with plastisol incorporated in casings and for sounding rockets, leveraging its and . These shifts ensured continued commercial viability amid evolving standards. In the 2020–2025 period, plastisol found niche growth in biomedical research, particularly as PVC-plastisol composites for tissue-mimicking phantoms in and MRI simulations, offering tunable acoustic and mechanical properties to replicate human soft tissues. The highlighted its role in printing durable graphics on (PPE), though studies raised concerns over phthalate from such plasticized materials into the and user exposure. As of 2023, the global plastisol market reached an estimated value of USD 23.55 billion, corresponding to annual consumption of approximately 500,000 tons, with major producers including Avient (formerly PolyOne) and driving supply through PVC-based formulations.

Applications

Screen Printing and Textiles

Plastisol is widely used in on textiles, where it is applied as a viscous paste through a screen onto fabrics such as , blends, and performance materials. The process involves depositing the in a single or multiple passes, often for efficiency, followed by curing in a conveyor dryer or heat press to fuse the PVC particles with the , forming a flexible that adheres to the fabric. Curing typically occurs at 160–180°C (320–356°F) for 1–3 minutes, ensuring the entire layer reaches the required for full fusion, which results in raised, opaque prints with a thickness of up to 250 microns depending on the and application technique. One key advantage of plastisol in textile screen is its , with properly cured prints resisting cracking and fading for up to 50–60 wash cycles under standard laundering conditions, making it suitable for high-volume garment production. The ink's composition allows for vibrant, opaque colors achieved through integration, enabling bright prints even on dark fabrics without the need for extensive underbasing in many cases. Additionally, its pseudoplastic supports high-density printing techniques, where multiple layers create three-dimensional effects like puff or raised designs, enhancing visual appeal and tactile interest on apparel. Modern plastisol formulations for include phthalate-free variants to meet environmental and regulatory standards, reducing potential risks while maintaining performance; as of 2022, these were used by approximately 45% of U.S. shops. Additives such as reducers or extenders are commonly incorporated at 2–5% by weight to optimize flow, prevent mesh clogging during extended runs, and achieve desired hand feel without compromising opacity. Introduced in the as a breakthrough over water-based inks, plastisol has become the predominant choice for garment , accounting for the majority of applications due to its ease and reliability, with hybrid methods—combining screen-printed underbases with overlays—emerging in the to support complex, full-color designs.

Molding and Casting

Plastisol is widely employed in slush molding to produce , flexible parts such as and automotive dashboards. In this process, a metal is preheated to approximately 180°C, after which liquid plastisol is poured into it. The mold is then rotated or placed on a to evenly the inner walls with the plastisol, allowing excess material to drain away as the heat causes the plastisol to gel and partially fuse. Upon cooling, the solidified part is removed, resulting in seamless objects with wall thicknesses typically ranging from 0.5 to 5 mm; the entire cycle, including heating, , and cooling, generally takes 5 to 10 minutes. A variant of slush molding, known as rotational molding, is used for larger items and involves bi-axial rotation of the mold to ensure uniform distribution of the plastisol during heating. The mold, often larger in scale than those used in standard slush molding, is filled with plastisol and rotated simultaneously around two perpendicular axes while heated to fuse the material, producing durable, hollow components without weld lines. This method is particularly suited for applications requiring consistent wall thickness and structural integrity in oversized parts. Uncured plastisol also serves as the basis for formulations, such as the brand introduced in the 1960s by , providing a non-hardening modeling material that remains pliable until cured. This clay, composed of PVC resin dispersed in plasticizers, allows for detailed sculpting and is hardened by at around 130°C for 15 to 30 minutes per 6 mm of thickness, depending on the formulation, to achieve a durable, flexible solid. Key advantages of plastisol molding and include low tooling costs compared to injection molding, as simple metal forms can be used without complex machinery, and the production of seamless parts that enhance and for detailed products. These processes enable cost-effective of intricate, flexible items while minimizing material waste through the drainage of excess plastisol.

Aerospace and Propellants

In solid rocket propellants, plastisol serves as a critical binder material, typically comprising 5-15% by weight of the formulation, which binds high concentrations of oxidizers such as ammonium perchlorate (often around 75% by weight) into composite fuels. This PVC-based binder imparts essential elasticity and adhesion properties, enabling the propellant to maintain structural integrity under the mechanical stresses of launch and flight while facilitating uniform combustion. The plastisol's castable nature allows for straightforward processing, where fine PVC particles are suspended in a plasticizer and mixed with oxidizer and fuel additives before curing. Historically, plastisol propellants gained prominence in the United States during the and , driven by advancements at organizations like the Atlantic Research Corporation. Early development began around 1955, with scale-up and testing leading to operational use by the late 1950s. Notable applications included sounding rockets such as the , a meteorological vehicle powered by an end-burning grain of plastisol-type solid that reached altitudes up to 200,000 feet. Tactical weapons, including man-portable air-defense systems like the Redeye, also employed PVC plastisol formulations for their reliable performance in compact motors. The of these propellants was precisely tuned by selecting specific types, such as dioctyl phthalate, which influenced stability and thrust profiles. Key properties making plastisol suitable for included its post-cure high tensile strength, often exceeding 5 in optimized formulations, which enhanced grain durability against vibrational loads. Additions of aluminum powder (typically 10-20% by weight) boosted to levels around 230-247 seconds, improving overall energy output without compromising castability. These attributes supported applications in control motors and auxiliary systems. By the , plastisol binders were largely phased out in favor of more mechanically robust and less hazardous alternatives like and , which offered superior aging stability and reduced toxicity concerns from HCl emissions. Despite this decline, the foundational principles of plastisol's dispersion and curing techniques continue to inform modern designs, particularly in castable fuel-oxidizer interfaces for experimental thrusters.

Toys, Crafts, and Recreation

Plastisol has been widely used in the toy industry since the 1960s, particularly in the production of flexible components by manufacturers like . Early dolls, introduced in 1959, were primarily constructed from (PVC) formulated as plastisol, which allowed for soft, durable limbs and torsos molded through processes such as . This material choice enabled the creation of poseable figures that mimicked human flexibility, though it was prone to degradation over time due to migration, resulting in a sticky surface on vintage pieces. By the 2000s, safety concerns over —common plasticizers in plastisol—prompted significant reforms in toy manufacturing. Mattel transitioned to non-phthalate alternatives, such as di(isononyl) cyclohexane-1,2-dicarboxylate (DINCH), for all products by 2009, reducing potential health risks associated with chemical leaching in children's toys. This shift aligned with broader regulatory pressures and ensured that modern plastisol-based dolls maintained flexibility without the toxicity issues of earlier formulations. In crafts, plastisol serves as the base for polymer clays, which are uncured suspensions of PVC resin and liquid plasticizers that remain pliable for sculpting. These materials, such as those in the Sculpey brand developed in 1967, can be shaped by hand and then cured in an at low temperatures (around 130°C) to form a flexible, durable solid without cracking. The plastisol formulation allows for easy incorporation of pigments and fillers, enabling artists to create detailed jewelry, miniatures, and decorative items that retain elasticity post-curing. Recreational fishing leverages plastisol for soft baits, where it is injection-molded into worm-like lures that mimic live prey through their lifelike texture and movement. These baits are formulated with added scents, pigments, and oils to enhance attractancy, achieving a soft, rubbery consistency that deforms realistically in . The for such plastic fishing baits exceeds $1 billion annually, driven by their and effectiveness in sports. In recent years, plastisol has found applications in recreation-related biomedical through tissue-mimicking phantoms for training and . Polyvinyl chloride plastisol (PVCP) phantoms, developed in studies from the , replicate the and acoustic of tissues like the liver or breast for and imaging practice. By tuning the formulation with fillers such as or oils, researchers achieve customizable mechanical (e.g., matching soft tissues) and values suitable for realistic wave propagation.

Automotive and Industrial Uses

In the automotive sector, plastisols are widely applied as underbody coatings to provide corrosion resistance, suppress road noise, and protect against stone impacts and debris. These coatings are typically sprayed or dipped onto vehicle chassis and undercarriage components, forming a flexible, durable barrier that adheres well to metal surfaces. For instance, in commercial vehicles like buses, plastisols have been used for protective seals and interior linings to enhance durability and reduce vibration. Additionally, dip-coated wires and hoses in road vehicles utilize plastisols for vibration damping, improving component longevity and passenger comfort by absorbing shocks and minimizing rattles. Beyond automotive applications, plastisols serve as coatings through dip-molding processes, where heated metal or plastic forms are immersed in liquid plastisol to create protective layers. This method is commonly employed for tool handles and industrial gloves, providing a non-slip, cushioned that enhances user and reduces hand during prolonged use. Plastisols also form corrosion-resistant films on metal parts, with typical thicknesses ranging from 0.2 to 2 mm, offering robust protection against in harsh settings such as chemical processing or equipment. Other industrial uses of plastisols include adhesives in for bonding materials like tiles, panels, and , where their heat-activated curing ensures strong, flexible joints resistant to . In electrical applications, plastisols provide for wires, connectors, and components, preventing short circuits and enhancing in high-voltage environments. However, adoption in electric vehicles has been limited by shifts toward lighter, non-PVC alternatives since around , driven by weight reduction needs and sustainability goals. Performance-wise, plastisols achieve UV resistance through the incorporation of stabilizers like (HALS), which inhibit and extend outdoor . Their flexibility spans a range of -20°C to 80°C, maintained by plasticizers that prevent in cold conditions while retaining elasticity at elevated temperatures.

Safety and Environmental Impact

Health and Safety Concerns

Plastisols, which are suspensions of polyvinyl chloride (PVC) particles in plasticizers, pose health risks primarily through the migration of phthalates such as di(2-ethylhexyl) phthalate (DEHP) from cured products into the human body. This leaching occurs as DEHP, a common plasticizer, migrates from the polymer matrix over time, especially under conditions of heat, abrasion, or contact with lipids, leading to potential dermal absorption or ingestion. Phthalates like DEHP are known endocrine disruptors, interfering with hormone systems and associated with reproductive disorders, developmental issues, and increased risk of certain cancers upon chronic exposure. To mitigate these risks in consumer products, regulatory measures have been implemented, notably under the European Union's REACH regulation, which since 2007 has restricted DEHP and other (including DBP and BBP) to a maximum concentration of 0.1% by weight in toys and childcare articles intended for children under three years old. During plastisol processing, workers face hazards from fume inhalation when the material is heated, as PVC degradation releases (HCl) gas, which irritates the , eyes, and mucous membranes, potentially causing coughing, chest tightness, and in severe cases. Skin contact with uncured plastisol can cause , dryness, or due to the solvents and plasticizers, necessitating the use of (PPE) such as gloves and protective clothing, along with adequate ventilation to control airborne contaminants. In end-use applications, such as food-contact items like PVC gloves, can migrate into food, raising concerns for dietary exposure and , with studies detecting DEHP levels exceeding safe thresholds in some vinyl products. During the , 2020 analyses of , including masks potentially printed with plastisol inks, revealed elevated phthalate concentrations, contributing to increased and dermal exposure risks for healthcare workers. Mitigation strategies include the development of low- (VOC) plastisol formulations that reduce emissions during curing and use alternative plasticizers to minimize phthalate content, thereby lowering overall exposure potential. Occupational safety guidelines from the (OSHA) establish a (PEL) for HCl of 5 as a value, enforceable through like local exhaust ventilation and respiratory protection to prevent overexposure in processing environments.

Environmental Regulations and Sustainability

Plastisol, a of (PVC) particles in plasticizers, poses significant environmental challenges in due to its non-biodegradable nature, leading to persistent accumulation in landfills and ecosystems. of plastisol waste can release highly toxic dioxins and furans if not conducted under strictly controlled conditions with advanced emission controls. efforts are hindered by contamination from plasticizers and additives, which complicate separation processes and result in low recovery rates for PVC-based materials, often below 10% globally. Regulatory frameworks address these issues by targeting , the primary plasticizers in traditional plastisols. In the United States, the Toxic Substances Control Act (TSCA) lists several , such as di(2-ethylhexyl) phthalate (DEHP) and (DBP), for and due to their environmental and , with prohibitions on their use in children's products exceeding 0.1%. In May 2025, the U.S. EPA released a draft for DEHP under TSCA, evaluating its risks to human health and the environment from industrial, commercial, and consumer uses, including in PVC products like plastisols. In the , the Restriction of Hazardous Substances () Directive bans four —DEHP, butyl benzyl phthalate (BBP), DBP, and (DIBP)—at concentrations above 0.1% in electrical and electronic equipment, including PVC components like plastisols, to enhance recyclability and reduce environmental release. The 2020s have seen a global push toward principles, exemplified by the development of bio-based plasticizers derived from vegetable oils, which offer compatibility with PVC while minimizing reliance on petroleum-derived . Sustainability initiatives focus on replacing to mitigate long-term ecological impacts. Research from 2023 to 2025 has advanced non-phthalate alternatives, such as adipate esters and bio-based compounds, which exhibit faster dissipation in and compared to traditional , reducing risks in aquatic systems. As of 2025, the PVC plastisol market is shifting toward phthalate-free and bio-based s, with innovations in low-temperature curing systems reducing energy use by 30-40%, supported by stricter environmental regulations. Lifecycle assessments of plastisol production and use indicate ranging from 2 to 5 kg CO₂ equivalent per kg of material, primarily from energy-intensive PVC synthesis and plasticizer processing, underscoring the need for low-carbon alternatives. Specific pollution incidents highlight plastisol's broader . Degraded soft plastic fishing lures, often made from plastisol, release into waterways, with studies detecting phthalate leaching rates up to 1001 ng/g and contributions to contamination that affect aquatic organisms. Additionally, from plastisol manufacturing facilities has been linked to localized chemical discharges, including plasticizers and solvents, contaminating surface waters and necessitating enhanced treatment protocols under environmental permits.

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