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We believe that you have got a better understanding about this concept. High Frequency Design. Understanding Mixers. From a Switching. Gary Breed. That's My Desire. Channing Diablos, Los. One primary condition for SIN is that the choice of monomer is restricted to compounds, which do not react together in the polymerization conditions. Hence, formation of both polymers by radical polymerization is not possible. Generally, one network is formed by radical polymerization, and the other one is obtained by polyaddition reaction.
The gel point of the two systems involved may be reached at the same time or may be shifted in time. In an extreme case, the formation of the first network is completed before the second monomer starts to react.
If both systems reach gelation simultaneously, a very fine state of phase dispersion may be obtained. If one monomer system reacts faster, a larger domain size is obtained and the mechanical properties of the SIN improve.
The three significant events that occur during the synthesis of SINs are gelation of polymer I, gelation of polymer II, and phase separation of polymer I from polymer II.
These three events may occur in any time order, and the number of independent ways of carrying out such a polymerization is 3! Each is expected to produce different morphologies and as a consequence a specific set of physical and mechanical properties . Studies were carried out on polyurethane-polymethyl methacrylate SIN  to determine how morphology develops from the initial mixture to the final IPN.
When the time lag between the onset of the two reactions is short, macroscopic phase separation occurs as the PU network is incompletely formed. However, when the time lag increases, PMMA forms a more continuous network, which limits. Reproduced from Polymer, Hence, by simply varying the lag time between the onset of the two reactions, quite different morphologies and, therefore, properties were obtained.
Sequential interpenetrating network Seq IPN : In sequential IPNs, the formation of undesired chemical bonds between separate networks is avoided because of the sequential synthesis. This broadens the probability of obtaining IPN from a wide range of starting materials. IPNs prepared by this technique are generally considered true IPNs if both the polymers are crosslinked. To obtain such an IPN, one polyfunctional monomer is first polymerized and crosslinked. The crosslinked polymer is then swollen in another monomer, which was previously mixed with its initiator and crosslinker.
The monomer was then crosslinked inside the existing polymer network. Among the factors such as miscibility of the polymer components, composition, crosslink density, polymerization sequence, polymerization, and phase separation kinetics-- which affect the phase morphology of sequential IPNs--the polymerization sequence is specifically important.
If polymers I and II are immiscible, and the crosslink density of I is small, i. However, the positions of the chains of monomer I will be hardly affected by the growth of network II if.
In such cases, network II will form by interpenetrating the existing network I, and a homogeneous IPN will result through forced compatibilization of both the polymers . Thorough study on the sequential IPN of immiscible polymers [e. However, increasing the crosslink density  may compatibilize these two components. It is shown that the key factor controlling the miscibility of sequential IPN is the crosslink density of the network that is polymerized first.
In an IPN, there may be some accidental grafts between the networks, but the deliberately introduced crosslinks should always outnumber the accidental grafts. The difference between the experimental and calculated values of the refractive index and the swelling degree of in situ sequential polyurethane PU -polystyrene PS IPNs shows the presence of additional physical crosslinks for such system with different combinations of PU and PS .
The maximum entanglement was achieved for a IPN composition. Sequential method results to the higher miscibility of the components compare to the simultaneous ones. On the other hand, in the in situ sequential process, the formation of a PU network is complete and the polymerization of styrene can only proceed in the immediate vicinity of the preformed PU network due to topological hindrance.
Therefore, higher miscibility of PU and PS results in a sequential technique . An interesting range of properties may be achieved when an elastomer and plastomer are blended in different proportions for the preparation of an IPN . A natural rubber polystyrene-based sequential IPN where the crosslinked NR phase was prepared first shows an intimate mixing of the two component phases, and a finer and more uniform distribution of PS in the NR phase was obtained .
Elastomer Crosslinking Elastomers are made of long chain molecules with molecular weight vary in the range of 1. Uncrosslinked elastomers have limited commercial value because of their easy deformation under load and rapid dissolution in different solvents.
To achieve the desired properties in the final products, it is necessary to crosslink the elastomers known as vulcanization. Sequential IPN. Simultaneous IPN. Reproduced from Macromol Symp, Hence, by vulcanization a raw rubber is transformed from its thermoplastic state to an elastic rubbery or hard ebonitelike state. The three-dimensional network structure imparts strength, rigidity and elastiticity, improves solvent properties, and enhances the resistance to deformation of elastomers under heat and cold.
Initially, vulcanization referred to the crosslinking of elastomer chains with the aid of sulfur but in due course different types of new crosslinking agents have been developed. The selection of crosslinking agents depends upon the type of elastomers and performance properties desired. Curing of the Rubber Stock and Stages of Vulcanization The curing and vulcanization of rubber are synonymous.
By plotting the change in a specific property such as tensile strength or modulus with the length of curing, the cure curve is obtained. The rate of vulcanization is an extremely important parameter in rubber industries as it controls the optimum cure time, which in turn determines the total batch cycles that may run per day in an industry. However, the rate of cure may be monitored by suitable choices of crosslinking agents and conditions. Vulcanization may occur in three different stages in an elastomer, which may be presented graphically by the generation of tensile modulus with time Figure 2.
The stages are the induction Warrior Is Back - I-Caze - Warrior Is Back (Vinyl), i. In the induction period, i. Stages of vulcanization. Compounds with rapid onset of vulcanization. Compounds with delayed onset of vulcanization. Compounds with increasing modulus. Compounds with reversion.
During this period, rubber compounds still flow uninhibited in the mold. This duration determines the safety of a stock against scorching premature vulcanization during the various processing steps, which precedes the final cure.
The choice of suitable crosslinking chemicals may shorten or lengthen the prevulcanization step. In most cases, the rapid vulcanization initiation is undesirable as it hampers the safe processing of the elastomer, but in some cases such as open curing, very fast vulcanization initiation is needed. The onset of vulcanization is followed by a crosslinking reaction at a rate dependent on the temperature and curative composition.
This is the prime step of vulcanization, when most of the desired technological properties of the vulcanizate generate. All the properties may not attain their best values at a specific time, and there is no universal method for the selection of optimum cure time.
Hence, for a specific formulation the time where the best combination of all the desired properties is achieved for a particular application is the optimum cure time. Further heating beyond the full cured state of the elastomer produces an overcured compound, which is evidenced either by continued stiffening reflected by a rise in modulus and a fall in elongation, or by reversion reflected by a fall in hardness, modulus and tensile strength, and a rise in elongation.
Overcure is unavoidable in the vulcanization of most of the products. The surface of a thick product becomes overcured until its interior reaches a full cured state. Any curing shorter than the optimum is known as undercure.
Scorching is the term used for premature vulcanization. It takes place due to improper selection of compounding and processing time and temperature. For thorough mixing of the compounding ingredients with the rubber stock, it is necessary to subject the rubber stock to a very high temperature for a definite time period in the mixing mill.
If vulcanization starts during this period, scorching occurs. Once scorching has occurred, the rubber stock cannot be processed further and its molding to its final shape is impossible. Hence, it is desirable that vulcanization should not start until the processing is complete, i.
Scorch resistance is the time elapsed before the vulcanization starts. Scorch resistance provides enough time for mixing, storing, and molding of the rubber mixture into the desired shape and size.
This can be achieved by the incorporation of a delayed action accelerator, which defers the onset of vulcanization and makes the compounding and processing operation safe. Temperature coefficient: The rate of vulcanization is highly dependent on temperature.
With the increase in temperature, the vulcanization rate increases. Vulcanization Modes and Mechanisms The choice of the vulcanization mode depends primarily upon the nature of the elastomer to be crosslinked.
Most of the elastomers are unsaturated in their nature, and for such polymers the predominant mode of crosslinking is sulfur vulcanization. The crosslink density depends upon the time and temperature of cure and the concentration of curatives as well as of cure sites. Sulfur vulcanization is not suitable for crosslinking of saturated elastomers, which may be crosslinked by peroxides or high-energy radiation.
Vulcanization with Sulfur Sulfur is the prime material for crosslinking the elastomers. The dose varies between 0. In addition to the polysulphide linkages results in intermolecular crosslinking, sulfur vulcanization leads to many undesirable side reactions such as formation of intramolecular cyclic structures that do not contribute to chain interlocking. Most of the evidence favors the free-radical mechanism for sulfur vulcanization.
The reaction steps are shown in Scheme 2. Free-radical mechanism of sulfur vulcanization. Reproduced from Prog Polym Sci, However, the use of sulfur alone is an inefficient process, as it needs a higher dose of sulfur, high temperature and long duration of vulcanization, and the predominant existence of polysulphide linkages rather than mono- or disulphide, which results in unsatisfactory strength and poor aging resistance of the vulcanizates.
Sometimes, instead of elemental sulfur, sulfur donors like dithio-di-morpholin, N-oxy diethylene dithiocarbamyl -N oxydiethylene sulphenamide, etc. They liberate sulfur at the vulcanization temperature and sometimes may act as vulcanization accelerators. Modified Sulfur Vulcanization Systems To overcome the disadvantages of elemental sulfur vulcanization, a modified sulfur vulcanization system that consists of sulfur, accelerator, and activator has been introduced, Warrior Is Back - I-Caze - Warrior Is Back (Vinyl).
The crosslink density of a vulcanized rubber is dependent on the nature of the elastomer, accelerator type and composition, time and temperature ratio, and the accelerator sulfur ratio . It is 0. Enhancement of accelerator-sulfur ratio results in a higher rate of crosslinking . The advantages of accelerator systems are 1. Accelerate the crosslinking reaction and hence reduce the cure time and make the process economic. Reduce the cure temperature and improve the aging stability.
Reduce the amount of organic sulfur and hence unwanted side reactions are mostly eliminated. Combination of two or more accelerators results in synergism and properties improve .
A broad plateau may be achieved in the stress heating time curve, indicating processing safety. Depending on their chemical nature, accelerators are classified as acidic or basic. Important acidic accelerators are as follows: Thiazole accelerators: They have highest economic importance in rubber compounding and are known as all-purpose accelerators. These accelerators impart safe processing with a broad vulcanization plateau and excellent aging resistance of the vulcanizates.
When combined with secondary basic accelerators such as guanidine, thiourea results in a higher crosslink density of the vulcanizates with an excellent synergism in product properties . Benzthiazole sulfenamide accelerators: Cyclohexyl- tert-butyl, and dicyclohexyl-benzthiazole sulfenamide are examples.
These accelerators impart a great processing safety as they start the vulcanization in retarded fashion. For molded articles they provide a long flow time but a very rapid vulcanization finish.
The addition of a secondary accelerator may synergistically affect the vulcanization speed , and a favorable combination of flow time and cure time may be achieved. Dithiocarbamate accelerators: Zinc, sodium or other metal dithiocarbamate are the examples. These are ultra-accelerators and to maintain processing safety, they are used in combination with other slow-acting accelerators. They may be used as sole accelerators in latex compounding , where the processing takes place at room temperature or in open curing.
Proper combinations with secondary accelerators allow their use even for transfer or injection molding. Xanthate accelerators: They are the derivatives of xanthic acid and are the fastest-acting accelerator. Hence they are used only in special cases of solid rubber.
Thiurams can be used for a wide range of sulfur accelerator ratio . Combination of thiurams as a secondary accelerator with rapid accelerators such as xanthate and dithiocarbamate, imparts a retarding effect without affecting the crosslink density of the vulcanizate, whereas the curing rate is enhanced with an accelerator such as thiazole .
These are secondary accelerators as they result in unfavorable vulcanization plateaus, have long scorch and vulcanization times, and products have poor aging resistance. In combination with primary accelerators such as mercapto, they show excellent synergistic action .
Aldehyde amine accelerators: These are the condensation products of aldehydes and amines. The principally used amine is aniline. They widely vary in their activities and are relatively less important accelerators.
Butyraldehydeaniline is a very rapid accelerator and leads to products of high crosslink density . Amine accelerators: These are secondary accelerators and rarely used alone. Cyclohexyl amine and dibutylamine are mostly used for the activation of dithiocarbamate accelerators. Activators: Zinc oxide has a pronounced effect Warrior Is Back - I-Caze - Warrior Is Back (Vinyl) sulfur vulcanization.
It improves the action of many accelerators and acts as an activator. Organic fatty acids such as stearic acid improve the action of ZnO.
Hence, in sulfur vulcanization, stearic acid accelerates the action of ZnO, which accelerates the actions of accelerators, which accelerates the action of sulfur.
The addition of ZnO enhances vulcanization efficiency and vulcanizate properties and reduces the vulcanization time. Introduction of nano-ZnO  results in lesser consumption of ZnO but higher improvement in the properties. General scheme for sulfur vulcanization. Reproduced from J Appl Polym Sci, Mode of reaction: The mechanism of vulcanization is fairly complex. It is mainly dependent on the components present, temperature, and duration of the process.
It has been proposed that the first step is the formation of an active accelerator complex I by the combination of accelerator and activator , which on subsequent reaction with sulfur produces an active sulfurating species II. This reactive species reacts with the allylic hydrogen atom of rubber unsaturations to form a rubber bound intermediate, designated as a crosslink precursor III. Reaction of such two intermediate moieties results in polysulfidic crosslinks IV. The initial crosslinks may eventually desulfurate to form shorter crosslinks V or degrade to cyclic sulphides.
The probable reactions are given in Scheme 2. Vulcanization Without Sulfur peroxide crosslinking Besides sulfur and accelerators, peroxides are also widely accepted today in rubber vulcanization. They are specifically used for rubber products requiring high thermal resistance.
Peroxides are mostly used for curing saturated elastomers i. The degree of crosslinking in peroxide vulcanization depends upon the radical yield from respective peroxide as well as the reactivity of the rubber.
Peroxide vulcanization involves three different stages [, ]. These three stages are homolytic cleavage of peroxide to form two alkoxy radicals, abstraction of the H- atom from a polymer chain by the alkoxy radical, and coupling of two radicals on adjacent polymer chains to form a C-C bond.
Hence, in peroxide vulcanization neither. The reaction mechanism is as follows:. For unsaturated elastomers, the primary radical formed by the decomposition of peroxide abstracts the hydrogen to the double bond [, ]. In peroxide vulcanization it is possible to apply a high vulcanization temperature without reversion. It is a rapid crosslinking process and the products possess good electrical and thermal properties. However, peroxides are expensive, and the products possess low tensile, tear strength, and poor abrasion resistance.
Peroxides may also react with other compounding ingredients such as antioxidants, plasticizers, or resins, etc. Important commercial peroxides are diacetyl peroxide, dibenzoyl peroxide, dicumylperoxide, di-tert-butyl peroxidetc [, ].
Such crosslinking does not involve use of any curative. Irradiation generates a high concentration of free radicals by dehydrogenation in the rubber molecules, which combine to form C-C crosslinks as in the case of peroxide crosslinling. It is a physically induced chemical reaction, which is easier and preferable for continuous curing technologies and is used for many applications in the rubber industry .
Halogenated compounds, nitrous oxide, sulfur monochloride, and bases such as amine and ammonia act as sensitizers in radiation crosslinking by reducing the required radiation dose and time . Thermal curing involves a long cure time, high-energy consumption, evolution of volatile toxic byproducts, and creates residual stresses in the material, whereas electron beam curing of rubber is a fast nonthermal process that utilizes highly energetic electrons at controlled doses for curing of variety of components for aerospace, automotive, and consumer applications .
Apart from crosslinking, electron beam radiation may also result in oxidation and degradation of a network structure . The crosslinking efficiency of a rubber under an electron beam depends on its molecular structure. The absorbed energy usually generates radicals, which can initiate the crosslinking reaction [, ].
Photosensitive groups include cinnamoyl, cinnamylidene, acryloyl, diazo and dithiocarbamate, and double bonds. Apart from the modes described above, unsaturated elastomers such as natural rubber, styrene butadiene rubber, or nitrile rubber may also be crosslinked by phenol formaldehyde resin [, ].
Ethylene thiourea has been established as a suitable crosslinker for specialty rubbers such as polychloroprene and epichlorohydrin rubbers [, ]. Fluororubbers may be crosslinked by polyamines, polyols, etc. The handling of common solvents is simple and the reaction process is smooth, but sometimes they are not environmentally friendly. Moreover, solvent removal from the final product creates additional wastes. To avoid these, supercritical CO2 is the alternative choice.
As supercritical fluid technology in recent years has made extraordinary progress in terms of commercial applications, its value in polymeric processes is obvious. CO2 is rather nontoxic, nonflammable, inexpensive, and volatile, as well as readily available. It can be easily separated from other components and has a readily accessible critical point Tc In addition, for both Sc and liquid CO2, the dielectric constant varies from 1. Low viscosity and surface tension makes the mass transfer speed is much faster than any other conventional liquid.
The density of sc CO2, and thus its solvent strength, is continuously tunable from gaslike to liquidlike by changing temperature or pressure . All these advantages make the CO2 an excellent reaction media for polymerization. The free-radical mechanism controls the grafting and crosslinking reaction is similar to the conventional one. Limitations: High-energy consumption and investment costs Using Radiation Routes Using High-Energy Radiation The use of high-energy radiation for the preparation of graft and crosslinked polymers began in early s and since then, it has been investigated in great depth.
The main radiation sources are for high-energy radiation and ion beam. Since radiation interacts with organic and other molecules to produce free radicals, cations, and anions, all three types of paths are possible.
The mechanisms are discussed below. Since monomers are not exposed to radiation in this technique, the obvious advantage is that it is relatively free from the problem of homopolymer formation. However, the disadvantage of the technique is that if the polymer is a degrading type, the scission of the base polymer due to its direct irradiation, brings about the formation of block rather than graft copolymers.
Also, if the substrate polymer does not have the ability to trap the radicals for a long enough time, subsequent grafting reaction will not follow. II Peroxidation Techniques Unlike the previous method, here the trunk polymer is subjected to high-energy radiation in the presence of air or oxygen. The stable peroxy products are then treated with the monomer at higher temperature, where the peroxides undergo decomposition to radicals, which then initiate grafting.
It is also seen that the peroxide method is also a preirradiation one with similar attendant advantages and disadvantages. The long. The monomer may be present as vapor, liquid, or solution. As both the monomer and substrate are exposed simultaneously to the radiation source, the formation of active sites in both the species occur. In practice, the radiation doses required to achieve graft in the simultaneous method are lower than the other two methods.
The reversible addition fragmentation transfer mechanism discussed earlier can also operate in the radiation initiated grafting technique [, ]. In the ionic mode, two different types cationic and anionic mechanisms can operate.
In a similar approach to that presented earlier, the polymer is irradiated to form polymeric ions and then reacts to the monomer. The high reaction rate of the ionic mode needs small radiation doses to make the requisite grafting sufficient. The cationic grafting is initiated from the backbone as follows:. The alternate cationic grafting mechanism proceeds through monomer radical cation, which subsequently forms a dimer.
Charge localization in the dimer occurs in such a way that the dimer radical cation reacts with the radical produced by the irradiation of the polymer to form the grafted polymer.
The mechanism is sketched below. Analogous mechanisms involve the anion as the initiator in cases of anionic grafting. Crosslinking also follows the same mechanistic way as grafting. It occurs between the same polymers as well as different polymers. The following reactions are expected to occur for the different polymers.
If one of the polymers is of the degrading type, one can still expect the formation of grafted structures such as. Using Photoradiation Photografting and crosslinking are usually considered radical chain reactions where the initiation step is produced by a photochemical event. For that, the feasibility of mosaic grafting also exists. Photoinitiated grafting is achieved by two different pathways: directly, i.
The chemical nature of the final product depends on the extent to which chain termination occurs via disproportionation versus combination. Actually, chain combination leads to crosslinks. The indirect method is illustrated in the routes for Warrior Is Back - I-Caze - Warrior Is Back (Vinyl) cases of attack on polymers by free radicals Route 1 and reaction of electronically excited photoinitiator molecules PI with lateral functional groups Route 2respec.
Actually, photoinitiator molecules are necessary where the monomers have low quantum yield. Route The photochemical processes of the photoinitiator that result in a transformation of the photoinitiator molecule often take place in the triplet states T. The transformation is mainly through cleavage processes, electron transfer reactions, hydrogen abstractions, isomerization, or rearrangement.
Thus the primary radical is produced. The produced primary radical will initiate the monomers to form graft polymers through the initiation, propagation, and termination reactions as in the usual free-radical polymerization. The free-radical photointiators are in general of two types: -cleavage photoinitiators and hydrogen abstraction photoinitiators.
This is a unimolecular one. The photochemical processes of this type of photoinitiators can be expressed as follows: 2 O Ph R OR. Hydrogen abstraction photoinitiators consist of an initiator and a coinitiator, i. The coinitiator is generally an amine, alcohol, or thiol with an -hydrogen and functions as the H-donor . The initiation mechanism is expressed as follows:. For example, benzophenones, thioxanthones, benzyls, etc. According to photodecomposition and the self-initiation mechanism , the acetone molecule on UV light, is either split by a Norrish type I reaction and form.
However, this is only occurred when acetone is in the vapor phase. Alcohol is used to promote photoinitiation efficiency. Photocrosslinking has also occurred through the free-radical mechanism as shown in grafting.
The reaction also occurs through pendant photofunctional groups Scheme 2. Metal ion initiated photocrosslinking is also feasible in the indirect approach . Using Plasma Radiation Plasmas are of neutral gaslike clouds or charged ion beams. They are typically formed by thermal, electrical, or light UV-light or intense visible light from a laser and ionizing a gas, stripping electrons away from atoms, thereby enabling the positive and negative charges to move freely.
In the chemical sense, the interactions with electrons, ions are radical generation reactions. The radical generation reaction is either hydrogen abstraction or chain scission reactions. Plasma is an initiator to cause grafting. Essentially, radicals formed in the polymer chains by plasma reactions undergo similar reactions to that high-energy irradiation.
The energy in plasma is lower than the usual conventional energy e-beam, -irradiation. The effects of the plasma are milder than those of high-energy irradiation, because of the low level of high activated species, electrons, and ions. Thus, the plasma forms free. Photocrosslinking in functionalized chalcone moiety. Reproduced from React Funct Polym, 49 1 : 77 As the changes are confined only to the depth of a few nanometers at the surface, the bulk properties degree of polymerization and crystallinity of the material are not very much influenced, with respect to high irradiation energy -irradiation, accelerated electrons.
Radical sites are formed as shown in high-energy radiation techniques, i. The preirra. Schematic diagram of pore-filling plasma-graft polymerization. Reproduced from J Membr Sci 95 1 Polymers are first exposed to plasma to create the radicals in the vicinity of the polymer surface, and then contacted to the vapor of the adequate monomer or the aqueous or organic solution of the monomer. Different plasmas are available, but for grafting, argon and oxygen plasma used the most.
It can be a single step reaction or a two-step reaction. The schematic presentation is given below Scheme 2. Polymer, J Polym Sci Polym Chem, Eur Polym J, 38 9 : Yener KM, Oguz O. Smart Mater Struc, Bhattacharyya SN, Maldas D.
Prog Polym Sc, Eur Polym J, J Macromol Sci Chem A, 16 6 : J Macromol Sci Chem A, 14 7 : J Appl Polym Sci, 27 5 : Trk J Chem, Chinese Chem Lett, 12 11 : Polym Int, 52 5 : J Appl Polym Sci, Bremner T, Rudin A.
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Polymer, 47 9 : React Funct Polym, Mequanint K, Sanderson R. Polym Test, Polym Test, 89 J Electron Spectrosc Relat Phenom, J Membr Sci, See more of Kowa Music Store on Facebook. Log In. Forgotten account? Not Now. Related Pages. FM Radio station. RagnaRok DJ. Strength of Unity Organisation. Rave Instinct Record label. Dedicated To The Core Record label. Pages liked by this Page. Industrial Strength Records. DJ Amisha. Recent post by Page. Kowa Music Store.
In the grafting of N-vinyl carboxamidomethylpropanesulfonic acid onto polystyrene with BPO, for example, a maximum in grafting was found at a BPO concentration of 30 mM . The more diffusion is inhibited, the lower this optimal radical flux will be. For example, the -initiated homopolymerization of vinyl imidazole was found to proceed at. Desire - Promo Detonated Presents Don Diablo - Take Off (WL) I-Caze - Warrior is Back Ich Haoj Renegade Outlaws Gotcha Dancin' (99 Rmx) (WL) The Samurai's Kunoichi wife (The men of Five Nations International Book 1) (Ricci's Renegade Warriors Book 1) Diablo's Desire Feb Shelli Quinn Kindle Edition. I-Caze - Warrior is Back Ignition Technician - The Pressure (WL) In the Air Tonight Insense - Grimlock / Pulsar Version (WL) Inshock C Interactive - Amok (WL) Into The Groove Italiaans Souvenir It's all True It's my life - It's my style Ivanhoe's Grote Avontuur Jade - Fantasy (WL) James Talk - Beef Curtains (WL) Jamez vs. X-Modman. Related to Warrior - Resurrected Warfare - Pure Filth From The Vaults Of Rabid Metal I-Caze - Warrior Is Back Resurrected - Resurrected The Beach Boys - High Water Hellbringer - Awakened From The Abyss.
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